U.S. patent application number 10/968216 was filed with the patent office on 2005-12-01 for curing accelerator for curing resin, curing resin composition, electronic component device and method for producing phosphine derivative.
Invention is credited to Katayose, Mitsuo, Nakamura, Kayoko, Nakamura, Shinya.
Application Number | 20050267286 10/968216 |
Document ID | / |
Family ID | 35426267 |
Filed Date | 2005-12-01 |
United States Patent
Application |
20050267286 |
Kind Code |
A1 |
Nakamura, Shinya ; et
al. |
December 1, 2005 |
Curing accelerator for curing resin, curing resin composition,
electronic component device and method for producing phosphine
derivative
Abstract
The invention relates to a curing accelerator for a curing resin
obtained by reacting a phosphine compound (a) with a compound (b)
having at least one halogen atom substituted on an aromatic ring
and at least one proton atom which can be discharged, and
subjecting the reaction product to dehydrohalogenation, a curing
resin composition containing the curing accelerator, and an
electronic component device having a device component encapsulated
with the curing resin composition. The curing accelerator exhibits
superior curability under moisture absorption, flow properties,
reflow cracking resistance and high-temperature storage
characteristics.
Inventors: |
Nakamura, Shinya;
(Tsukuba-shi, JP) ; Katayose, Mitsuo;
(Tsukuba-shi, JP) ; Nakamura, Kayoko; (Colmar,
FR) |
Correspondence
Address: |
ANTONELLI, TERRY, STOUT & KRAUS, LLP
1300 NORTH SEVENTEENTH STREET
SUITE 1800
ARLINGTON
VA
22209-3873
US
|
Family ID: |
35426267 |
Appl. No.: |
10/968216 |
Filed: |
October 20, 2004 |
Current U.S.
Class: |
528/408 |
Current CPC
Class: |
C08G 59/688
20130101 |
Class at
Publication: |
528/408 |
International
Class: |
C08G 059/68 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 20, 2003 |
JP |
2003-359335 |
Claims
1. A curing accelerator for a curing resin obtained by reacting a
phosphine compound (a) with a compound (b) having at least one
halogen atom substituted on an aromatic ring and at least one
proton atom which can be discharged, and subjecting the reaction
product to dehydrohalogenation.
2. The curing accelerator for the curing resin according to claim
1, wherein the phosphine compound (a) is represented by the
following general formula (I). 26(wherein R.sup.1 to R.sup.3in the
formula (I) represent a hydrogen atom, or a substituted or
unsubstituted hydrocarbon group having 1 to 18 carbon atoms, and
each may be the same or different. Two or more of R.sup.1 to
R.sup.3 may be mutually bonded to form a cyclic structure.)
3. The curing accelerator for the curing resin according to any one
of claims 1, 2, wherein the compound (b) having at least one
halogen atom substituted on the aromatic ring and at least one
proton atom which can be discharged is represented by the following
general formula (II). 27(wherein R.sup.4 to R.sup.7 in the formula
(II) represent a hydrogen atom or a monovalent organic group having
1 to 18 carbon atoms, and each may be the same or different. YH
represents a monovalent group having 0 to 18 carbon atoms and at
least one proton which can be discharged. X represents a halogen
atom. Two or more of R.sup.4to R.sup.7 and YH may be mutually
bonded to form a cyclic structure.)
4. The curing accelerator for the curing resin according to claim
3, wherein the compound (b) having at least one halogen atom
substituted on the aromatic ring and at least one proton atom which
can be discharged has a phenolic hydroxyl group.
5. The curing accelerator for the curing resin according to claim
2, wherein R.sup.1 to R.sup.3 in the general formula (I) are a
monovalent substituent group selected from the group consisting of
an alkyl group and an aryl group which does not have a phenolic
hydroxyl group or a mercapto group.
6. A curing resin composition comprising: at least one kind of the
curing accelerator for the curing resin (A) according to any one of
claims 1 to 5; and a curing resin (B).
7. The curing resin composition according to claim 6, wherein the
curing resin (B) contains an epoxy resin (C).
8. The curing resin composition according to any one of claims 6 to
7, further comprising a curing agent (D).
9. The curing resin composition according to any one of claims 6 to
7, further comprising inorganic filler (E).
10. The curing resin composition according to claim 7, wherein the
epoxy resin (C) contains at least one kind of epoxy resin selected
from the group consisting of a biphenyl type epoxy resin, a
stilbene type epoxy resin, a diphenylmethane type epoxy resin, a
sulfur atom content type epoxy resin, a novolac type epoxy resin, a
dicyclopentadiene type epoxy resin, a salicylaldehyde type epoxy
resin, a copolymer type epoxy resin of naphthol and cresol, and an
epoxidized material of an aralkyl type phenolic resin.
11. The curing resin composition according to claim 8, wherein the
curing agent (D) contains at least one kind selected from the group
consisting of an aralkyl type phenolic resin, a dicyclopentadiene
type phenolic resin, a salicylaldehyde type phenolic resin, a
copolymer type resin of a benzaldehyde type phenolic resin and the
aralkyl type phenolic resin, and a novolac type phenolic resin.
12. An electronic component device comprising a device component
encapsulated with the curing resin composition according to any one
of claims 6 to 11.
13. A method for producing a phosphine derivative comprising the
steps of: reacting a phosphine compound (a) with a compound (b)
having at least one halogen atom substituted on an aromatic ring
and at least one proton atom which can be discharged to produce a
phosphonium halide; and subjecting the phosphonium halide to
dehydrohalogenation.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The invention relates to a curing accelerator for a curing
resin, a curing resin composition using the curing accelerator,
suitable for molding materials, laminated sheet materials or
adhesive materials, an electronic component device provided with
device components encapsulated with the curing resin composition,
and a method for obtaining a phosphine derivative used for the
curing accelerator.
[0003] 2. Description of the Related Art
[0004] Curing resins such as an epoxy resin are conventionally used
in a wide range as molding materials, laminated sheet materials and
adhesive materials. Since these curing resins require rapid
curability from the viewpoint of the productivity improvement,
compounds for accelerating the curing reaction, that is, curing
accelerators are widely used. Of the curing resins, especially,
epoxy resin compositions are in wide use in the field of the
encapsulation of device components in electronic components such as
transistors and ICs. This is because the epoxy resin has properties
such as molding properties, electrical properties, moisture
resistance, heat resistance, mechanical properties and adhesion to
component inserts which are well balanced. Especially, the
combination of an o-cresol novolak type epoxy resin and a phenol
novolac curing agent excels in these balances, and is preferably
used as a base resin for the molding material for IC encapsulation.
Amine compounds such as a third amine and imidazole and phosphorus
compounds such as phosphines and phosphonium are generally used as
the curing accelerator in the epoxy resin compositions.
[0005] The high density mounting on printed circuit boards of
electronic components has been recently advanced, and, therefore,
surface-mounted packages have become mainstream in place of
conventional pin inserting type packages in the electronic
components. In the surface-mounted ICs such as ICs and LSIs, the
occupation volume of the component to the package gradually is
increased so as to improve the mounting density, and the thickness
of the package has been extremely thin. In the pin inserting type
packages, after pins are inserted through the wiring board,
soldering is performed from the back of the wiring board, and
thereby, the package is not exposed directly to high temperatures.
On the other hand, after the surface-mounted type ICs are
temporarily attached to the surface of the wiring board, the
surface-mounted type ICs are treated by a solder bus and a reflow
device or the like, and thereby, the surface-mounted type ICs are
exposed directly to soldering temperatures. As a result, when the
IC package absorbs moisture, the absorbing moisture expands rapidly
at the time of soldering, resulting in the package crack,
therefore, this has become the great problem.
[0006] So as to improve the reflow cracking resistance to the
package crack at the time of the soldering, so-called the flow
properties crack, epoxy resin compositions containing a lot of
inorganic fillers are proposed. However, since the increasing
amount of the inorganic filler causes the decrease in flow
properties at the time of molding, faulty filling, faulty
conduction due to breaking of bonding wires of IC chips, and the
performance of molded products may lower, there is a limit in the
increasing amount of the inorganic filler. As a result, this
technique can not be expected to bring about any remarkable
improvement in the reflow cracking resistance. Particularly, when
the amine system curing accelerators such as phosphorus type curing
accelerators such as triphenylphosphine, amine type curing
accelerators such as 1,8-diazabicyclo [5.4.0]undecene-7 are used,
the flow properties is low, and thereby this technique can not be
expected to bring about any remarkable improvement in the reflow
cracking resistance.
[0007] So as to overcome such a problem, it is proposed that an
addition product of triphenylphosphine with 1,4-benzoquinone be
used as a curing accelerator (see, Japanese Patent Application
Laid-Open (JP-A) No. 9-157497). When the addition product is used
as the curing accelerator, there is a problem in curability when
the resin composition is exposed to air, in a word, curability
under moisture absorption. When the molding material having poor
curability under moisture absorption absorbs moisture from air at
the time of manufacturing, transporting and using, troubles such as
gate break, chip crack, the reduction of releasability are easily
caused. Also, problems exist in that the difference of the air
humidity at the time of manufacturing transporting and using,
particularly, and the molding performance is not stable due to the
difference of the season. Moreover, a problem in that rapid
curability is bad, and the resin composition is not cured in a
short time when an organic phospholam compound (see, JP-A
No.11-60906) proposed as a curing accelerator having steady
curability is used. So as to overcome such a problem, it is
proposed that an addition product of a phosphine compound in which
at least one alkyl group is bonded with a phosphorus atom and a
quinone compound is used as the curing accelerator (see, JP-A Nos.
2002-3574 and 2002-80563).
[0008] However, a problem exists in that when a package
encapsulated with the curing resin composition used as the curing
accelerator is exposed to high temperature, electrical continuity
defect is easily generated in the package, that is, the package has
poor high-temperature storage characteristics. The present
invention was made taking account of the problems discussed above.
It is an object of the present invention to provide a curing
accelerator for a curing resin which exhibits superior curability
under moisture absorption, flow properties, reflow cracking
resistance and high-temperature storage characteristics, a method
for obtaining a phosphine derivative used for the curing
accelerator, a curing resin composition using the curing
accelerator, and an electronic component device having a device
component encapsulated with the curing resin composition.
SUMMARY OF THE INVENTION
[0009] The inventors have conducted earnest studies to solve the
aforementioned problems. As a result, the present inventors have
discovered that the curing resin composition having superior
curability under moisture absorption, flow properties, reflow
cracking resistance can be obtained by using a specific phosphorus
compound as the curing accelerator, and the aforementioned object
can be achieved. Thus these have accomplished the present
invention.
[0010] That is, the invention relates to the following.
[0011] (1) A curing accelerator for a curing resin obtained by
reacting a phosphine compound (a) with a compound (b) having at
least one halogen atom substituted on an aromatic ring and at least
one proton atom which can be discharged, and subjecting the
reaction product to dehydrohalogenation.
[0012] (2) The curing accelerator for the curing resin according to
the above (1), wherein the phosphine compound (a) is represented by
the following general formula (I). 1
[0013] (wherein R.sup.1 to R.sup.3 in the formula (I) represent a
hydrogen atom, or a substituted or unsubstituted hydrocarbon group
having 1 to 18 carbon atoms, and each may be the same or different.
Two or more of R.sup.1 to R.sup.3 may be mutually bonded to form a
cyclic structure.)
[0014] (3) The curing accelerator for the curing resin according to
any one of the above (1), (2), wherein the compound (b) having at
least one halogen atom substituted on the aromatic ring and at
least one proton atom which can be discharged is represented by the
following general formula (II). 2
[0015] (wherein R.sup.4 to R.sup.7 in the formula (II) represent a
hydrogen atom or a monovalent organic group having 1 to 18 carbon
atoms, and each may be the same or different. YH represents a
monovalent group having 0 to 18 carbon atoms and at least one
proton which can be discharged. X represents a halogen atom. Two or
more of R.sup.4 to R.sup.7 and YH may be mutually bonded to form a
cyclic structure.)
[0016] (4) The curing accelerator for the curing resin according to
the above (3), wherein the compound (b) having at least one halogen
atom substituted on the aromatic ring and at least one proton atom
which can be discharged has a phenolic hydroxyl group.
[0017] (5) The curing accelerator for the curing resin according to
the above (2), wherein R.sup.1 to R.sup.3 in the general formula
(I) are a monovalent substituent group selected from the group
consisting of an alkyl group and an aryl group which does not have
a phenolic hydroxyl group or a mercapto group.
[0018] (6) A curing resin composition comprising: at least one kind
of the curing accelerator for the curing resin (A) according to any
one of the above (1) to (5); and a curing resin (B).
[0019] (7) The curing resin composition according to the above (6),
wherein the curing resin (B) contains an epoxy resin (C).
[0020] (8) The curing resin composition according to any one of the
above (6) to (7), further comprising a curing agent (D).
[0021] (9) The curing resin composition according to any one of the
above (6) to (7), further comprising inorganic filler (E).
[0022] (10) The curing resin composition according to the above
(7), wherein the epoxy resin (C) contains at least one kind of
epoxy resin selected from the group consisting of a biphenyl type
epoxy resin, a stilbene type epoxy resin, a diphenylmethane type
epoxy resin, a sulfur atom content type epoxy resin, a novolac type
epoxy resin, a dicyclopentadiene type epoxy resin, a
salicylaldehyde type epoxy resin, a copolymer type epoxy resin of
naphthol and cresol, and an epoxidized material of an aralkyl type
phenolic resin.
[0023] (11) The curing resin composition according to the above
(8), wherein the curing agent (D) contains at least one kind
selected from the group consisting of an aralkyl type phenolic
resin, a dicyclopentadiene type phenolic resin, a salicylaldehyde
type phenolic resin, a copolymer type resin of a benzaldehyde type
phenolic resin and the aralkyl type phenolic resin, and a novolac
type phenolic resin.
[0024] (12) An electronic component device comprising a device
component encapsulated with the curing resin composition according
to any one of the above (6) to (11).
[0025] (13) A method for producing a phosphine derivative
comprising the steps of: reacting a phosphine compound (a) with a
compound (b) having at least one halogen atom substituted on an
aromatic ring and at least one proton atom which can be discharged
to produce a phosphonium halide; and subjecting the phosphonium
halide to dehydrohalogenation.
[0026] The curing accelerator for a curing resin of the invention
has superior curability under moisture absorption, flow properties,
reflow cracking resistance and high-temperature storage
characteristics. The curing resin composition using the curing
accelerator for the curing resin has superior curability under
moisture absorption and flow properties. The electronic component
devices having superior reflow cracking resistance,
high-temperature storage characteristics and reliability can be
obtained by encapsulating the electronic component parts such as IC
and LSI with the curing resin composition, promising a great
industrial value.
BRIEF DESCRIPTION OF THE DRAWINGS
[0027] FIG. 1 is the .sup.1H-NMR spectrum of a compound 1 obtained
by Example of the invention;
[0028] FIG. 2 is the .sup.13C-NMR spectrum of a compound 1 obtained
by Example of the invention;
[0029] FIG. 3 is the .sup.31P-NMR spectrum of a compound 1 obtained
by Example of the invention;
[0030] FIG. 4 is the IR spectrum of a compound 1 obtained by
Example of the invention;
[0031] FIG. 5 is the .sup.1H-NMR spectrum of a compound 2 obtained
by Example of the invention;
[0032] FIG. 6 is the .sup.13C-NMR spectrum of a compound 2 obtained
by Example of the invention;
[0033] FIG. 7 is the .sup.31P-NMR spectrum of a compound 2 obtained
by Example of the invention;
[0034] FIG. 8 is the IR spectrum of a compound 2 obtained by
Example of the invention;
[0035] FIG. 9 is the .sup.1H-NMR spectrum of a compound 3 obtained
by Example of the invention;
[0036] FIG. 10 is the .sup.13C-NMR spectrum of a compound 3
obtained by Example of the invention;
[0037] FIG. 11 is the .sup.31P-NMR spectrum of a compound 3
obtained by Example of the invention;
[0038] FIG. 12 is the IR spectrum of a compound 3 obtained by
Example of the invention;
[0039] FIG. 13 is the .sup.1H-NMR spectrum of a compound 4 obtained
by Example of the invention;
[0040] FIG. 14 is the .sup.13C-NMR spectrum of a compound 4
obtained by Example of the invention;
[0041] FIG. 15 is the .sup.31P-NMR spectrum of a compound 4
obtained by Example of the invention;
[0042] FIG. 16 is the IR spectrum of a compound 4 obtained by
Example of the invention;
[0043] FIG. 17 is the .sup.1H-NMR spectrum of a compound 5 obtained
by Example of the invention;
[0044] FIG. 18 is the .sup.13C-NMR spectrum of a compound 5
obtained by Example of the invention;
[0045] FIG. 19 is the .sup.31P-NMR spectrum of a compound 5
obtained by Example of the invention;
[0046] FIG. 20 is the IR spectrum of a compound 5 obtained by
Example of the invention;
[0047] FIG. 21 is the .sup.1H-NMR spectrum of a compound 6 obtained
by Example of the invention;
[0048] FIG. 22 is the .sup.13C-NMR spectrum of a compound 6
obtained by Example of the invention;
[0049] FIG. 23 is the .sup.31P-NMR spectrum of a compound 6
obtained by Example of the invention;
[0050] FIG. 24 is the IR spectrum of a compound 6 obtained by
Example of the invention;
[0051] FIG. 25 is the .sup.1H-NMR spectrum of a compound 7 obtained
by Example of the invention;
[0052] FIG. 26 is the .sup.13C-NMR spectrum of a compound 7
obtained by Example of the invention;
[0053] FIG. 27 is the .sup.31P-NMR spectrum of a compound 7
obtained by Example of the invention; and
[0054] FIG. 28 is the IR spectrum of a compound 7 obtained by
Example of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0055] There are no particular limitations on the curing
accelerator (A) for the curing resin of the invention, as long as
the curing accelerator can be obtained by reacting a phosphine
compound (a) with a compound (b) having at least one halogen atom
substituted on an aromatic ring and at least one proton atom which
can be discharged, and then subjecting the reaction product to
dehydrohalogenation.
[0056] There are no particular limitations on the phosphine
compounds (a), as long as the compounds are producible. For
instance, examples thereof include the compounds represented by the
following general formula (I). 3
[0057] (wherein R.sup.1 to R.sup.3 in the formula (I) represent a
hydrogen atom, or a substituted or unsubstituted hydrocarbon group
having 1 to 18 carbon atoms, and each may be the same or different.
Two or more of R.sup.1 to R.sup.3 may be mutually bonded to form a
cyclic structure.)
[0058] Though R.sup.1 to R.sup.3 in the general formula (I)
represent a hydrogen atom, or a substituted or unsubstituted
hydrocarbon group having 1 to 18 carbon atoms, there are no
particular limitations on the substituted or unsubstituted
hydrocarbon group having 1 to 18 carbon atoms.
[0059] Examples of the substituted or unsubstituted hydrocarbon
groups include a substituted or unsubstituted aliphatic hydrocarbon
group having 1 to 18 carbon atoms, a substituted or unsubstituted
alicyclic hydrocarbon group having 1 to 18 carbon atoms, and a
substituted or unsubstituted aromatic hydrocarbon group having 1 to
18 carbon atoms.
[0060] Examples of the substituted or unsubstituted aliphatic
hydrocarbon groups having 1 to 18 carbon atoms include: alkyl
groups such as a methyl group, an ethyl group, a propyl group, an
iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl
group, a pentyl group, a hexyl group, a octyl group, a decyl group,
a dodecyl group; allyl groups; vinyl groups; and an aliphatic
hydrocarbon group obtained by substituting them with an alkyl
group, an alkoxy group, an aryl group, a hydroxyl group, an amino
group and a halogen or the like.
[0061] Examples of the substituted or unsubstituted alicyclic
hydrocarbon groups having 1 to 18 carbon atoms include a
cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a
cyclopentenyl group, a cyclohexenyl group, and an alicyclic
hydrocarbon group obtained by substituting them with an alkyl
group, an alkoxy group, an aryl group, an aryloxy group, a hydroxyl
group, an amino group and a halogen or the like.
[0062] Examples of the substituted or unsubstituted aromatic
hydrocarbon groups having 1 to 18 carbon atoms include aryl groups
such as a phenyl group and a tolyl group; alkyl group-substituted
aryl groups such as a dimethyl phenyl group, an ethyl phenyl group,
a butyl phenyl group and a tert -butyl phenyl group; alkoxy
group-substituted aryl groups such as a methoxy phenyl, an ethoxy
phenyl group, buthoxy phenyl group and a tert-buthoxy phenyl group;
and an aromatic hydrocarbon group obtained by substituting them
with an alkyl group, an alkoxy group, an aryl group, an aryloxy
group, an amino group and a halogen or the like.
[0063] It is preferable that R.sup.1 to R.sup.3 are a monovalent
substituent group selected from the group consisting of an alkyl
group and an aryl group which does not have a phenolic hydroxyl
group or a mercapto group. In particular, from the viewpoint of the
availability of phosphine, R.sup.1 to R.sup.3 are preferably
selected from the group consisting of an unsubstituted, or alkyl
group or alkoxy group substituted phenyl group, such as a phenyl
group, a p-tolyl group, a m-tolyl group, an o-tolyl group, a
p-methoxy phenyl, a m-methoxy phenyl and an o-methoxy phenyl or the
like; and a linear or cyclic alkyl group such as a methyl group, an
ethyl group, a propyl group, an iso-propyl group, a butyl group, a
sec-butyl group, a tert-butyl group, an octyl group and a
cyclohexyl group or the like.
[0064] Of the phosphine compounds represented by the general
formula (I), triphenylphosphine; diphenyl(alkylphenyl)phosphine
such as diphenyl-p-tolylphosphine; diphenyl(alkoxyphenyl)phosphine
such as diphenyl-p-anisylphosphine; and
phenylbis(alkylphenyl)phosphine such as phenyldi-p-tolylphosphine
are preferable from the viewpoint of the reflow cracking
resistance. From the viewpoint of the curability under moisture
absorption, tris(alkylphenyl)phosphine such as
tri-p-tolylphosphine, tri-o-tolylphosphine and
tri-m-tolylphosphine; tris(alkoxyphenyl)phosphin- e such as
tri-p-anisylphosphine; phenylbis(alkoxyphenyl)phosphine such as
phenyldi-p-anisylphosphine; alkyldiarylphosphine such as
n-butyldiphenylphosphine and cyclohexyldiphenylphosphine;
dialkylarylphosphine such as di-n-butylphenylphosphine and
dicyclohexylphenylphosphine; and trialkylphosphine such as
tri-n-butylphosphine, tricyclohexylphosphine, tri-n-octylphosphine,
trimethyphosphine, triethylphosphine, truisopropylphosphine and
tricyclopentylphosphine are preferable.
[0065] There are no particular limitations on the compounds (b)
having at least one halogen atom substituted on the aromatic ring
and at least one proton atom which can be discharged, as long as
the compounds are producible. For instance, examples thereof
include the compounds represented by the following general formula
(II). 4
[0066] (wherein R.sup.4 to R.sup.7 in the general formula (II)
represent a hydrogen atom or a monovalent organic group having 1 to
18 carbon atoms, and each may be the same or different. YH
represents a monovalent group having 0 to 18 carbon atoms and at
least one proton which can be discharged. X represents a halogen
atom. Two or more of R.sup.4to R.sup.7 and YH may be mutually
bonded to form a cyclic structure.)
[0067] Though R.sup.4 to R.sup.7 in the general formula (II)
represent a hydrogen atom or a monovalent organic group having 1 to
18 carbon atoms, there are no particular limitations on the
monovalent organic group of 1 to 18 carbon atoms. Examples include
substituted or unsubstituted aliphatic hydrocarbon groups having 1
to 18 carbon atoms, substituted or unsubstituted alicyclic
hydrocarbon groups having 1 to 18 carbon atoms, substituted or
unsubstituted aromatic hydrocarbon groups having 1 to 18 carbon
atoms, substituted or unsubstituted aliphatic, alicyclic or
aromatic oxy groups having 1 to 18 carbon atoms, substituted or
unsubstituted aliphatic, alicyclic or aromatic carbonyl groups
having 1 to 18 carbon atoms, substituted or unsubstituted
aliphatic, alicyclic or aromatic oxycarbony groups having 1 to 18
carbon atoms, and substituted or unsubstituted aliphatic, alicyclic
or aromatic carbonyoxy groups having 1 to 18 carbon atoms.
[0068] Substituted or unsubstituted aliphatic hydrocarbon groups,
alicyclic hydrocarbon groups and aromatic hydrocarbon groups having
1 to 18 carbon atoms are described above.
[0069] The substituted or unsubstituted aliphatic, alicyclic or
aromatic oxy groups having 1 to 18 carbon atoms include; aliphatic
oxy groups such as a methoxy group, an ethoxy group, a propoxy
group, an isopropoxy group, an n-butoxy group, a sec-butoxy group,
a tert-butoxy group, a cyclohexyloxy group, an allyloxy group, a
vinyloxy group; aromatic oxy groups such as a phenoxy group, a
methylphenoxy group, an ethylphenoxy group, a methoxyphenoxy group,
a butoxyphenoxy group and a phenoxyphenoxy group; and ones obtained
by substituting an alkyl group, an alkoxy group, an aryl group, an
aryloxy group, an amino group and a halogen or the like
therefor.
[0070] The substituted or unsubstituted aliphatic, alicyclic or
aromatic carbonyl groups having 1 to 18 carbon atoms include;
aliphatic carbonyl groups such as a formyl group, an acetyl group,
an ethyl carbonyl group, a butyryl group, a cyclohexyl carbonyl
group and an allyl carbonyl; aromatic carbonyl groups such as a
phenyl carbonyl group and a methylphenyl carbonyl group; and ones
obtained by substituting an alkyl group, an alkoxy group, an aryl
group, an aryloxy group, an amino group and a halogen or the like
therefor.
[0071] The substituted or unsubstituted aliphatic, alicyclic or
aromatic oxycarbony groups having 1 to 18 carbon atoms include
aliphatic oxycarbonyl groups such as a methoxycarbonyl group, an
ethoxycarbonyl group, a butoxycarbonyl group, an allyloxycarbonyl
group and a cyclohexyloxycarbonyl group; aromatic oxycarbonyl
groups such as a phenoxycarbonyl group and amethylphenoxycarbonyl
group; and ones obtained by substituting an alkyl group, an alkoxy
group, an aryl group, an aryloxy group, an amino group and a
halogen or the like therefor.
[0072] The substituted or unsubstituted aliphatic, alicyclic or
aromatic carbonyoxy groups having 1 to 18 carbon atoms include
aliphatic carbonyoxy groups such as a methylcarbonyoxy group, an
ethylcarbonyoxy group, a butylcarbonyoxy group, an allylcarbonyoxy
group, a cyclohexylcarbonyoxy group; aromatic carbonyoxy groups
such as a phenylcarbonyoxy group and a methylphenylcarbonyoxy
group; and ones obtained by substituting an alkyl group, an alkoxy
group, an aryl group, an aryloxy group, an amino group and a
halogen or the like therefor.
[0073] When two or more of R.sup.4 to R.sup.7 in the formula (II)
form the cyclic structure, examples thereof include
1-bromo-2-naphthol and 4-chloro-1-naphthol. However, there are no
particular limitations thereon.
[0074] YH in the formula (II) represents a monovalent group having
0 to 18 carbon atoms and at least one proton which can be
discharged. There are no particular limitations on the monovalent
groups having 0 to 18 carbon atoms and at least one proton which
can be discharged. Examples thereof include: a group in which a
hydrogen atom is bonded to a 16th atom such as a hydroxyl group, a
mercapto group and a hydroseleno group; a group which has a
carboxyl group and has 1 to 18 carbon atoms, such as a carboxyl
group, a carboxymethyl group, a carboxyethyl group, a carboxyphenyl
group and a carboxynaphthyl group; and a group which has a phenolic
hydroxyl group and has 1 to 18 carbon atoms, such as a
hydroxyphenyl group, a hydroxyphenylmethyl group, a hydroxynaphthyl
group, a hydroxyfuryl group, a hydroxythienyl group and a
hydroxypyridyl group.
[0075] When YH in the formula (II) forms a cyclic structure with
any one of R.sup.4 to R.sup.7, examples thereof include
6-bromo-2-naphthol. However, there are no particular limitations
thereon.
[0076] Examples of the compounds which are represented by the
general formula (II), and have at least one halogen atom
substituted on the aromatic ring and at least one proton which can
be discharged include: compounds having a carboxylic acid such as
4-bromobenzoic acid, 3-bromobenzoic acid, 2-bromobenzoic acid,
4-chlorobenzoic acid, 3-chlorobenzoic acid, 2-chlorobenzoic acid,
4-iodo benzoic acid, 3-iodo benzoic acid, 2-iodo benzoic acid,
4-bromophenylacetic acid, 3-bromophenylacetic acid,
2-bromophenylacetic acid, 4-chlorophenyl acetic acid,
3-chlorophenyl acetic acid and 2-chlorophenyl acetic acid;
compounds having a phenolic hydroxyl group such as 4-bromophenol,
3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol,
2-chlorophenol, 4-iodophenol, 3-iodo phenol, 2-iodo phenol,
4-bromo-2-methylphenol, 4-bromo-3-methylphenol,
4-bromo-2,6-dimethylpheno- l, 4-bromo-3,5-dimethylphenol,
4-bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol,
1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl,
bromohydroxypyridine, bromohydroxyfuran and bromohydroxythiophene;
and compounds havingathiol such as 4-bromothiol, 3-bromothiol,
2-bromothiol, 4-chlorothiol and bromothionaphthol.
[0077] Particularly, compounds having a phenolic hydroxyl group
such as 4-bromophenol, 3-bromophenol, 2-bromophenol,
4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4- iodo phenol, 3-
iodo phenol, 2- iodo phenolic, 4-bromo-2-methylphenol,
4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol,
4-bromo-3,5-dimethylphenol, 4-bromo-2,6-di-tert-butylphenol,
4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol,
4-bromo-4'-hydroxybiphenyl, bromohydroxypyridine, bromohydroxyfuran
and bromohydroxythiophene are preferable from the viewpoint of the
moisture absorption curability.
[0078] The method for producing phosphine derivative of the
invention is a method for producing a phosphine derivative which
can be used as the curing accelerator (A) for the curing resin. The
method comprises the steps of: reacting a phosphine compound (a)
(hereinafter, referred to as "compound (a)") with a compound (b)
(hereinafter, referred to as "compound (b)") having at least one
halogen atom substituted on an aromatic ring and at least one
proton atom which can be discharged to produce a phosphonium
halide; and subjecting the phosphonium halide to
dehydrohalogenatdion.
[0079] There are no particular limitations on the method of the
invention, as long as the method has a process and a reactive
condition in which the compound (a) is reacted with the compound
(b) to produce the phosphonium halide and the phosphonium halide is
then subjected to dehydrohalogenation. The reaction between the
compound (a) and the compound (b), and the dehydrohalogenation
reaction may proceed in one step or in more than two steps. The
phosphine derivative may be produced in one pot or in more than two
pots.
[0080] The compound (a) can be reacted with the compound (b) by
using a coupling catalyst or the like in case of necessity.
[0081] Examples of the coupling catalysts which can be used
include: halogenated nickels such as nickel chloride(II) and nickel
bromide (II); halogenated cobalts such as cobalt chloride (II) and
cobalt bromide (II); and a nickel compound having a phosphine as
ligand such as tris(triphenylphosphine)nickel. There are no
particular limitations on the coupling catalysts as long as the
coupling catalysts can react the compound (a) with the compound
(b).
[0082] The compound (a) can be reacted with the compound (b) by
using techniques such as the irradiation of ultraviolet rays in
case of necessity.
[0083] Examples of the compounds (b) which can be reacted by using
the technique of the irradiation of ultraviolet rays include the
compounds (b) in which the halogen atom is iodide such as 4-iodo
phenol, 3-iodo phenol, 2-iodo phenol, 4-iodo benzoic acid, 3-iodo
benzoic acid, 2-iodo benzoic acid. However, there are no particular
limitations on the compounds (b), as long as the compounds can be
reacted by the technique.
[0084] So as to subject the product obtained by reacting the
compound (a) with the compound (b) to dehydrohalogenation, reagents
for aiding the dehydrohalogenation reaction can be optionally used.
Examples of the reagents include basic compounds such as
lithiumhydroxide, sodium hydroxide, potassium hydroxide, rubidium
hydroxide, cesium hydroxide, beryllium hydroxide, magnesium
hydroxide, calcium hydroxide, strontium hydroxide, barium
hydroxide, sodium carbonate, calcium carbonate, rubidium carbonate,
cesium carbonate, sodium bicarbonate, potassium hydrogen carbonate,
triethylamine, tributylamine, pyridine, pyrazine,
1,5-diazabicyclo[4.3.0]nonene-5, 1,8-diazabicyclo[5.4.0]undecene-7.
However, there are no particular limitations on the reagents, as
long as the reagents aid the dehydrohalogenation reaction.
[0085] Examples of the curing accelerators (A) for the curing resin
which can be obtained by subjecting the product produced by
reacting the compound (a) with the compound (b) to
dehydrohalogenation include the compounds represented by the
following general formula (III). However, there are no particular
limitations thereon. 5
[0086] Wherein R.sup.1 to R.sup.3 and R.sup.4 to R.sup.7 in the
formula (III) are the same as those in the formulae (I) and (II).
Y.sup.- represents a group formed by releasing one proton from a
monovalent group having 0 to 18 carbon atoms and at least one
proton which can be discharged. Two or more of R.sup.4 to R.sup.7
and Y.sup.- may be mutually bonded to form a cyclic structure.
[0087] Examples of the compounds represented by the general formula
(III) includes a compound which can be represented by the following
resonance formula (IV). 6
[0088] (wherein, R.sup.1 to R.sup.7 and Y.sup.- in the formula (IV)
are common to those of the above-mentioned. Two or more of R.sup.4
to R.sup.7 and Y.sup.- or Y may be bonded to have a ring
structure.)
[0089] Examples of the compounds which can be represented by the
resonance formula (IV) include a compound in which Y.sup.- in the
general formula (III) is located at ortho position or para position
for P.sup.+, and an element bonding to the ortho position or the
para position has lone pair electron ,such as a compound which is
represented by the following resonance formula (V) or (VI).
However, there are no particular limitations on the compound. For
instance, the lone pair electron may be conjugated as represented
by the following resonance formula (VII) or (VIII). 7
[0090] (wherein, R.sup.1 to R.sup.7 in the formulae (V) and (VI)
are common to those of the above-mentioned. Z- represents a group
in which one proton is discharged from a monovalent group having 0
to 18 carbon atoms and having at least one proton capable of being
discharged and the atom bonded to a benzene ring has a conjugated
or a nonconjugated lone pair electron. Two or more of R.sup.4 to
R.sup.7 and Z.sup.- or Z may be bonded to have a ring structure.)
8
[0091] (wherein, R.sup.1 to R.sup.7, Z.sup.- and Z in the formulae
(VII) and (VIII) are common to those in the above formulae (V) and
(VI). R.sup.51 to R.sup.57 represent a hydrogen atom or a
substituted or unsubstituted monovalent organic group having 1 to
18 carbon atoms, and each may be the same or different. Two or more
of R.sup.4 to R.sup.7, R.sup.51 to R.sup.57 and Z.sup.- or Z may be
bonded to have a ring structure.)
[0092] Examples of the compounds which cannot be represented by the
resonance formula (IV) include a compound in which Y.sup.- of the
general formula (III) is located at meta position for P.sup.+, and
a compound in which Y.sup.- bonds to ortho position or para
position for P.sup.+ and in which the atom bonded do not have lone
pair electron, such as a compound which is represented by the
following resonance formula (IX) or (X). However, there are no
particular limitations on the compound. 9
[0093] (wherein, R.sup.1 to R.sup.7in the formulae (IX), (X) and
Z.sup.- in the formulae (IX) are common to those of the
above-mentioned, . W.sup.- in the formula (X) represents a group in
which one proton is discharged from a monovalent group having 0 to
18 carbon atoms and having at least one proton capable of being
discharged and the atom bonded to a benzene ring has no lone pair
electron. Two or more of R.sup.4 to R.sup.7, Z.sup.- and W.sup.-
may be bonded to have a ring structure.)
[0094] The curing resin composition of the invention contains at
least of one kind of a curing accelerator (A) for a curing resin of
the invention and a curing resin (B).
[0095] There are no particular limitations on the curing resins (B)
used in the invention as long as the curing accelerator (A)
accelerates curing. Examples thereof include an epoxy resin, a
phenolic resin, a silicon resin, an amino resin, an unsaturated
polyester resin, a diallyl phthalate resin and an alkyd resin, and
these may be used alone or in combination of two or more types. In
particular, the epoxy resin (C) is particularly preferable from the
viewpoint that the effect of the curing accelerator (A) is
sufficiently exhibited.
[0096] When the epoxy resin is used as ingredients (B), the epoxy
resin having at least two epoxy groups in one molecule can be used.
Such epoxy resins are not limited to the following, and examples
thereof include: novolac type epoxy resins including a phenol
novolac type epoxy resin, an o-cresol novolak type epoxy resin
obtained by epoxidizing a novolak resin obtained by subjecting
phenols such as phenol, cresol, xylenol, resorcinol, catechol,
bisphenol A or bisphenol F and/or naphthols such as
.alpha.-naphthol, .beta.-naphthol and dihydroxynaphthalene, and the
compound which has an aldehyde group such as formaldehyde,
acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde to
condensation or cocondensation in the presence of an acid
catalyst;
[0097] diglycidyl ethers of phenol compounds such as bisphenol A,
bisphenol F, bisphenol S, an alkyl-substituted or non-substituted
biphenol and a stilbene system phenol (bisphenol type epoxy resins,
biphenyl type epoxy resins and stilbene type epoxy resins or the
like);
[0098] glycidyl ethers of alcohols such as butanediol, polyethylene
glycol and polypropylene glycol;
[0099] glycidyl ester type epoxy resins of carboxylic acids such as
phthalic acid, isophthalic acid and tetrahydrophthalic acid;
[0100] glycidyl type or methylglycidyl type epoxy resins obtained
by substituting an active hydrogen bonded to the nitrogen atom of
aniline or isocyanuric acid with a glycidyl group;
[0101] alicyclic epoxy resins obtained by epoxidizing the olefinic
bond in the molecule, such as vinylcyclohexene diepoxide,
3,4-epoxycylcohexylmeth- yl-3,4-epoxycylcohexane carboxylate,
and
[0102]
2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane;
[0103] glycidyl ethers of paraxylylene and/or metaxylylene modified
phenolic resins;
[0104] glycidyl ethers of terpene modified phenolic resin;
[0105] glycidyl ethers of dicyclopentadiene modified phenolic
resins;
[0106] glycidyl ethers of cyclopentadiene modified phenolic
resins;
[0107] glycidyl ethers of polycyclic aromatic-ring modified
phenolic resin;
[0108] glycidyl ethers of naphthalene-ring-containing phenolic
resin;
[0109] halogenated phenol novolak type epoxy resins;
[0110] hydroquinone type epoxy resins;
[0111] trimethylolpropane type epoxy resins;
[0112] linear aliphatic epoxy resins obtained by oxidazing the
olefinic bond with a peracid such as an peracetic acid;
[0113] diphenylmethane type epoxy resins;
[0114] epoxidized materials of aralkyl type phenolic resins such as
phenol aralkyl resins and naphthol aralkyl resins; and
[0115] sulfur atom content type epoxy resins.
[0116] These may be used alone or in combination of two or more
types. A biphenyl type epoxy resin, a stilbene type epoxy resin, a
diphenylmethane type epoxy resin, a sulfur atom content type epoxy
resin, a novolac type epoxy resin, a dicyclopentadiene type epoxy
resin, a salicylaldehyde type epoxy resin, the copolymer type epoxy
resin of naphthols and phenols, an epoxidized material of an
aralkyl type phenolic resin are preferable from the viewpoint the
reflow cracking resistance and the flow properties in the epoxy
resins. Particularly, 4,4'-bis(2,3-epoxypropoxy)-3,3',5,5'-tetr-
amethybiphenyl is more preferable from the viewpoint of the reflow
cracking resistance, and 4,4'-bis(2,3-epoxypropoxy)-biphenyl is
preferable from the viewpoint of molding properties and heat
resistance. A biphenyl type epoxy resin, a stilbene type epoxy
resin, a diphenylmethane type epoxy resin, a sulfur atom content
type epoxy resin, a novolac type epoxy resin, a dicyclopentadiene
type epoxy resin, a salicylaldehyde type epoxy resin, the copolymer
type epoxy resins of naphthols and phenols, and an epoxidized
material of aralkyl type phenolic resin may be used alone or in
combination of two or more types. In order for their performance to
be exhibited, these may preferably be used in an amount of at least
30% by weight in total based on the total weight of the epoxy
resin, and particularly preferably used in an amount of at least
50% by weight.
[0117] There are no particular limitations on the biphenyl type
epoxy resins as long as the epoxy resins have a biphenyl skeleton,
and the epoxy resin represented by the following general formula
(XI) is preferable. Among the epoxy resin represented by the
following general formula (XI), YX-4000H (trade name; manufactured
by Japan Epoxy Resins Co., Ltd) in which 3,3',5,5' positions are
the methyl group when the positions in which the oxygen atoms are
substituted among R.sup.8 are made 4,4' position, the others are
the hydrogen atoms can be obtained as a marketed commodity. And
4,4'-bis (2,3-epoxypropxy) biphenyl in which all of R.sup.8 are the
hydrogen atoms or the like can be obtained as a marketed commodity.
YL-6121H (trade name; manufactured by Japan Epoxy Resins Co., Ltd)
can be also obtained as a marketed commodity, which is the mixture
of the case that 3, 3',5, 5' positions are the methyl group when
the positions in which the oxygen atoms are substituted among
R.sup.8 were made 4,4' position, the others are the hydrogen atoms
and the case that all of R.sup.8 are the hydrogen atoms. 10
[0118] (wherein, R.sup.8 in the general formula (XI) represents a
hydrogen atom or an alkyl group having 1 to 12 carbon atoms or an
aryl group having 4 to 18 carbon atoms, and each may be the same or
different. n is a mean value, and represents a positive number of 0
to 10.)
[0119] There are no particular limitations on the stilbene type
epoxy resins, as long as the epoxy resins have a stilbene skeleton.
The epoxy resin represented by the following general formula (XII)
is preferable. Among the epoxy resin represented by the following
general formula (XII), ESLV-210 (trade name; manufactured by Japan
Epoxy Resins Co., Ltd) which is the mixture of the case that
3,3',5,5' positions are the methyl group when the positions in
which the oxygen atoms are substituted among R.sup.9 are made 4,4'
position, the others are the hydrogen atoms, and all of R.sup.10
are the hydrogen atoms, and the case that three positions are the
methyl groups, one position is the tert-butyl group, the others are
the hydrogen atoms among 3,3',5,5' positions, and all of R.sup.10
are the hydrogen atoms or the like can be obtained as a marketed
commodity. 11
[0120] (wherein, R.sup.9, R.sup.10 in the general formula (XII)
represent a hydrogen atom or a monovalent organic group which
having 1 to 18 carbon atoms, and each may be the same or different.
n is a mean value, and represents a positive number of 0 to
10.)
[0121] There are no particular limitations on the diphenylmethane
type epoxy resins, as long as the epoxy resins have a
diphenylmethane skeleton. The epoxy resin represented by the
following general formula (XIII) is preferable. Among the epoxy
resin represented by the following general formula (XIII),
YSLV-80XY (trade name; manufactured by Nippon Steel Chemical Co.,
Ltd.) in which 3,3',5,5' positions are the methyl group and the
other are the hydrogen atoms when the positions in which the oxygen
atoms are substituted among R.sup.12 are made 4,4' position and all
of R.sup.11 are the hydrogen atoms or the like can be obtained as a
marketed commodity. 12
[0122] (wherein, R.sup.11, R.sup.12 in the general formula (XIII)
represent a hydrogen atom or a monovalent organic group having 1 to
18 carbon atoms, and each may be the same or different. n is a mean
value, and represents a positive number of 0 to 10.)
[0123] There are no particular limitations on the sulfur atom
content type epoxy resins, as long as the epoxy resins contain a
sulfur atom. Examples thereof include the epoxy resin represented
by the following general formula (XIV). Among the epoxy resin
represented by the following general formula (XIV), YSLV-120TE
(trade name; manufactured by Nippon Steel Chemical Co., Ltd.) in
which 3,3' position are the tert-butyl group, 6,6' position are a
the methyl group, and the other are the hydrogen atoms when the
positions in which the oxygen atoms are substituted among R.sup.13
are made 4,4' position or the like can be obtained as a marketed
commodity. 13
[0124] (wherein, R.sup.13 in the general formula (XIV) represents a
hydrogen atom or a monovalent organic group which having 1 to 18
carbon atoms, and each may be the same or different. n is a mean
value, and represents a positive number of 0 to 10.)
[0125] There are no particular limitations on the novolac type
epoxy resins, as long as the epoxy resins are obtained by
epoxidizing the novolac type phenolic resin. It is preferable that
the epoxy resins are obtained by epoxidizing novolac type phenolic
resins such as phenol novolac, cresol novolac and naphthol novolac
using a technique for glycidyletherizing or the like. For instance,
the epoxy resin represented by the following general formula (XV)
is more preferable. ESCN-190 and ESCN- 195 (trade name;
manufactured by Sumitomo Chemical Co., Ltd.) in which all of
R.sup.14 are the hydrogen atoms in the epoxy resins represented by
the following general formula (XV) and R.sup.15 is the methyl group
(i=1) or the like can be obtained as a marketed commodity. 14
[0126] (wherein, R.sup.14, R.sup.15 in the general formula (XV)
represent a hydrogen atom or a monovalent organic group having 1 to
18 carbon atoms, and each may be the same or different. i is an
integer of 0 to 3; n is a mean value, and represents a positive
number of 0 to 10.)
[0127] There are no particular limitations on the dicyclopentadiene
type epoxy resins, as long as the epoxy resins are obtained by
epoxidizing a compound having a dicyclopentadiene skeleton as a raw
material. The epoxy resin represented by the following general
formula (XVI) is preferable. HP-7200 (trade name; manufactured by
Dainippon Ink And Chemicals, Incorporated) which is i=0 in the
epoxy resins represented by the following general formula (XVI) or
the like can be obtained as a marketed commodity. 15
[0128] (wherein, R.sup.16 in the general formula (XVI) represents a
hydrogen atom or a monovalent organic group having 1 to 18 carbon
atoms, and each may be the same or different. i is an integer of 0
to 3; n is a mean value, and represents a positive number of 0 to
10.)
[0129] There are no particular limitations on the salicylaldehyde
type epoxy resins, as long as the epoxy resins are obtained by
using a compound having a salicylaldehyde skeleton as a raw
material. The salicylaldehyde type epoxy resins such as the epoxy
resins obtained by glycidyletherizing the salicylaldehyde type
phenolic resin such as the novolac type phenolic resins of the
compound which has the compound having the salcylaldehyde skeleton
and a compound having a phenolic hydroxyl group is preferable, and
the epoxy resin represented by the following general formula (XVII)
is more preferable. MEH-7500 (trade name; manufactured by Meiwa
Plastic Industries, Ltd.) which is i=0 and k=0 in the epoxy resins
represented by the following general formula (XVII) or the like can
be obtained as a marketed commodity. 16
[0130] (wherein, R.sup.17, R.sup.18 in the general formula (XVII)
represent a hydrogen atom or a monovalent organic group having 1 to
18 carbon atoms, and each may be the same or different. i is an
integer of 0 to 3; k is an integer of 0 to 4; n is a mean value,
and represents a positive number of 0 to 10.)
[0131] There are no particular limitations on the copolymer type
epoxy resins of naphthols and phenols, as long as the epoxy resins
are obtained by using a compound having a naphthol skeleton and a
compound having a phenol skeleton as a raw material. It is
preferable that the copolymer type epoxy resins are obtained by
glycidyletherizing the novolac type phenolic resins using the
compound having the naphthol skeleton and the compound having the
phenol skeleton. The epoxy resin represented by the following
general formula (XVIII) is more preferable. NC-7300 (trade name;
manufactured by Nippon Kayaku Co., Ltd.) which is i=0, j=0 and k=0
in the epoxy resins represented by the following general formula
(XVIII) or the like can be obtained as a marketed commodity. 17
[0132] (wherein, R.sup.19 to R.sup.21 in the general formula
(XVIII) represent a hydrogen atom or a monovalent organic group
having 1 to 18 carbon atoms, and each may be the same or different.
i is an integer of 0 to 3: ; is an integer of 0 to 2; k is an
integer of 0 to 4. p is a mean value, and represents a positive
number of 0 to 1. l, m are a mean value, and represents a positive
number of 0 to 11. (l+m) represents a positive number of 1 to
11.)
[0133] Examples of the epoxy resins represented by the general
formula (XVIII) include a random copolymer which contains 1 pieces
of constituent units and m pieces of constituent units at random,
an alternating copolymer containing alternately, a copolymer
containing regularly, and a block copolymer containing into a
block. Any one kind of these may be used alone or in combination of
two or more types.
[0134] There are no particular limitations on the epoxidized
materials of the aralkyl type phenolic resin such as the phenol
aralkyl resin and the naphthol aralkyl resin as long as the
epoxidized materials are obtained by using the phenolic resins
synthesized from phenols such as phenol and cresol and/or naphthols
such as naphothol and dimethylnaphothol, and dimethoxyparaxylene,
bis(methoxymethyl) biphenyl and their derivatives as a raw
material. It is preferable that the epoxidized materials are
obtained by glycidyletherizing the phenolic resins synthesized from
phenols such as phenol and cresol and/or naphthols such as
naphothol and dimethylnaphothol, and dimethoxyparaxylene, bis
(methoxymethyl) biphenyl and their derivatives. The epoxy resin
represented by the following general formula (XIX) and (XX) is more
preferable. NC-3000S (trade name; manufactured by Nippon Kayaku
Co., Ltd.) and CER-3000 (trade name; manufactured by Nippon Kayaku
Co., Ltd.) or the like can be obtained as a marketed commodity in
the epoxy resins represented by the following general formula
(XIX). In the NC-3000S, i=0, and R.sup.23 are the hydrogen atoms.
The CER-3000 is obtained by mixing the epoxy resin in which i=0,
and R.sup.23 are the hydrogen atoms, and the epoxy resin in which
all R.sup.8 of the general formula (XI) are hydrogen atoms in a
ratio of 80/20 by weight. ESN-175 (trade name; manufactured by
Nippon Steel Chemical Co., Ltd.) or the like can be obtained as a
marketed commodity in the epoxy resins represented by the following
general formula (XX). In the ESN-175, j=0, k of R.sup.25=0, and k
of R.sup.26=0. 18
[0135] (wherein, R.sup.22 to R.sup.26 in the general formulae
(XIX), (XX) represent a hydrogen atoms or a monovalent organic
group having 1 to 18 carbon atoms, and each may be the same or
different. n is a mean value, and represents a positive number of 0
to 10. i is an integer of 0 to 3: j is an integer of 0 to 2: k is
an integer of 0 to 4. K of R.sup.25 and k of R.sup.26 may be the
same or different.)
[0136] That each of R.sup.8 to R.sup.26 in the general formulae
(XI) to (XX) may be the same or different means, for instance, that
all of R.sup.8 of 8 to 88 in the formula (XI) may be the same or
different. For the others R.sup.9 to R.sup.26, all of each number
included in the formula may be the same or different. Each of
R.sup.8 to R.sup.26 may be the same or different. For instance, all
of R.sup.9, R.sup.10 may be the same or different.
[0137] Letter symbol n in the general formulae (XI) to (XX) is
within the range of 0 to 10. When it is more than 10, the component
(B) has a high melt viscosity and hence the curing resin
composition also has a high viscosity at the time of its melt
molding, tending to cause faulty filling and deformation of bonding
wires (i.e., gold wires which connect device components with
leads). It is preferable that the average n in one molecule is set
within the range of 0 to 4. The values of i, j, k in the general
formulae (XV) to (XX) are independent for each number of each
R.
[0138] A curing agent (D) can be optionally used for the curing
resin composition. When the epoxy resin is used as the curing resin
(B), there are no particular limitations on the curing agents which
can be used as long as the curing agents can cure the epoxy resin.
Examples thereof include phenolic compounds such as phenolic
resins, amine compounds such as diamine and polyamine, organic acid
anhydrides such as phthalic anhydride, trimellitic anhydride and
pyromellitic anhydride, and carboxylic acid compounds such as
dicarboxylic acid and polycarboxylic acid. These may be used alone
or in combination of two or more types. In particular, the phenolic
resin is preferable from the viewpoint that the effect of the
curing accelerator (A) is sufficiently exhibited.
[0139] There are no particular limitations on the phenolic resin
used as the curing agent (D) of the epoxy resin. Examples thereof
include a compound which is the phenolic resin having the phenolic
hydroxyl groups of 2 or more in one molecule used generally and has
two phenolic hydroxyl groups in one molecule such as resorcinol,
catechol, bisphenol A, bisphenol F, and alkyl-substituted or
non-substituted bisphenol;
[0140] a novolac type phenolic resin obtained by subjecting phenols
such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A,
bisphenol F, phenylphenol, aminophenol, and/or naphthols such as
.alpha.-naphthol, .beta.-naphthol, dihydroxynaphthalene, and
aldehydes such as formaldehyde, acetaldehyde, propionaldehyde,
benzaldehyde and salicylaldehyde to condensation or cocondensation
in the presence of an acid catalyst;
[0141] an aralkyl type phenolic resin such as phenol aralkyl resins
and naphthol aralkyl resins synthesized from phenols and/or
naphthols, and dimethoxyparaxylene and bis(methoxymethyl)
biphenyl;
[0142] paraxylylene and/or methaxylylene modified phenolic
resin;
[0143] melamine modified phenolic resin;
[0144] terpene modified phenolic resin;
[0145] dicyclopentadiene type phenolic resin and dicyclopentadiene
type naphthol resin synthesized by the copolymerization from
phenols and/or naphthols and dicyclopentadiene;
[0146] cyclopentadiene modified phenolic resin;
[0147] polycyclic aromatic-ring modified phenolic resin;
[0148] biphenyl type phenolic resin;
[0149] triphenylmethane type phenolic resin; and
[0150] the phenolic resins obtained by the copolymerization of two
or more of these types. These may be used alone or in combination
of two or more types.
[0151] The aralkyl type phenolic resin, the dicyclopentadiene type
phenolic resin, the salicylaldehyde type phenolic resin, the
copolymer type phenolic resin of the benzaldehyde type and the
aralkyl type, and the novolac type phenolic resin are preferable
from the viewpoint of the reflow cracking resistance in these
phenolic resins. The aralkyl type phenolic resin, the
dicyclopentadiene type phenolic resin, the salicylaldehyde type
phenolic resin, the copolymer type phenolic resin of the
benzaldehyde type and the aralkyl type, and the novolac type
phenolic resin may be used alone or in combination of two or more
types. In order for their performance to be exhibited, these may
preferably be used in an amount of at least 30% by weight in total
based on the total weight of the phenolic resin, and more
preferably 50% by weight.
[0152] There are no particular limitations on the aralkyl type
phenolic resins as long as the resins are synthesized from phenols
and/or naphthols and dicyclopentadiene, bis(methoxymethyl) biphenyl
and their derivatives. The phenolic resins represented by the
general formulae (XXI) to (XXIII) are preferable.
[0153] XL-225, XLC (trade name; manufactured by Mitsui Chemicals
Co., Ltd.), and MEH-7800 (trade name; manufactured by Meiwa Plastic
Industries, Ltd.) or the like can be obtained as a marketed
commodity in the phenolic resins represented by the following
general formula (XXI). In XL-225, XLC and MEH-7800, i=0, and
k=0.
[0154] MEH-7851 (trade name; Meiwa Plastic Industries, Ltd.) or the
like in the phenolic resins represented by the following general
formula (XXII) can be obtained as a marketed commodity. In the
MEH-7851, i=0 and all of R.sup.30 are the hydrogen atoms.
[0155] SN-170 (trade name; manufactured by Nippon Steel Chemical
Co., Ltd.) or the like in the phenolic resins represented by the
following general formula (XXIII) can be obtained as a marketed
commodity. In SN-170, j=0, k of R.sup.32=0, and k of R.sup.33=0.
19
[0156] (wherein, R.sup.27 to R.sup.33 in the general formulae (XXI)
to (XXIII) represent a hydrogen atom or a monovalent organic group
having 1 to 18 carbon atoms, and each may be the same or different.
i is an integer of 0 to 3; k is an integer of 0 to 4; j is an
integer of 0 to 2. n is a mean value, and represents a positive
number of 0 to 10. k of R.sup.32 and k of R.sup.33 may be the same
or different.)
[0157] There are no particular limitations on the dicyclopentadiene
type phenolic resins as long as the phenolic resins are obtained by
using a compound having a dicyclopentadiene skeleton as a raw
material. The phenolic resin represented by the following general
formula (XXIV) is preferable. DPP (trade name; manufactured by
Nippon Petrochemicals Co., Ltd.) or the like in the phenolic resin
represented by the following general formula (XXIV) can be obtained
as a marketed commodity. In DPP, i=0. 20
[0158] (wherein, R.sup.34 in the general formula (XXIV) represents
a hydrogen atom or a monovalent organic group having 1 to 18 carbon
atoms, and each may be the same or different. i is an integer of 0
to 3: n is a mean value, and represents a positive number of 0 to
10.
[0159] There are no particular limitations on the salicylaldehyde
type phenolic resins as long as the phenolic resins are obtained by
using a compound having a salicylaldehyde skeleton as a raw
material. The phenolic resin represented by the following general
formula (XXV) is preferable.
[0160] MEH-7500 (trade name; manufactured by Meiwa Plastic
Industries, Ltd.) or the like can be obtained as a marketed
commodity in the phenolic resins represented by the following
general formula (XXV). In MEH-7500, i=0, and k=0. 21
[0161] (wherein, R.sup.35, R.sup.36 in the general formula (XXV)
represent a hydrogen atom or a monovalent organic group having 1 to
18 carbon atoms, and each may be the same or different. i is an
integer of 0 to 3; k is an integer of 0 to 4; n is a mean value,
and represents a positive number of 0 to 10. )
[0162] There are no particular limitations on the copolymer type
phenolic resins of the benzaldehyde type and the aralkyl type, as
long as the copolymer type phenolic resins of the aralkyl type
phenolic resin and the phenolic resin obtained by using a compound
having a benzaldehyde skeleton as a raw material. The phenolic
resin represented by the following general formula (XXVI) is
preferable.
[0163] HE-510 (trade name; manufactured by Sumitomo Metal
Industories Ltd.) or the like can be obtained as a marketed
commodity in the phenolic resin represented by the following
general formula (XXVI). In HE-510, i=0, k=0, and q=0. 22
[0164] (wherein, R.sup.37 to R.sup.39 in the general formula (XXVI)
represent a hydrogen atom or a monovalent organic group having 1 to
18 carbon atoms, and each may be the same or different. i is an
integer of 0 to 3: k is an integer of 0 to 4: q is an integer of 0
to 5: 1, m are mean values, and represent a positive number of 0 to
11 respectively. (1+m) represents a positive number of 1 to
11.)
[0165] There are no particular limitations on the novolac type
phenolic resins, as long as the phenolic resins are obtained by
subjecting phenols and/or naphthols and aldehydes to condensation
or cocondensation in the presence of an acid catalyst. The phenolic
resin represented by the following general formula (XXVII) is
preferable.
[0166] TAMANOL758, 759 (trade name; manufactured by Arakawa
chemical Industries, Ltd.) and HP-850N (trade name; manufactured by
Hitachi Chemical Co., Ltd.) or the like can be obtained as a
marketed commodity in the phenolic resins represented by the
following general formula (XXVII). In TAMANOL758, 759 and HP-850N,
i=0 and all of R.sup.40 are the hydrogen atoms. 23
[0167] (R.sup.40 and R.sup.41 in the general formula (XXVII)
represent a hydrogen atom or a monovalent organic group having 1 to
18 carbon atoms, and each may be the same or different. i is an
integer of 0 to 3; k is an integer of 0 to 4; n is a mean value,
and represents a positive number of 0 to 10.)
[0168] That each of R.sup.27 to R.sup.41 in the general formulae
(XXI) to (XXVII) may be the same or different means, for instance,
that all of R.sup.27 of i pieces in the formula (XXI) may be the
same or different. For the others R.sup.28 to R.sup.41, All of each
number included in the formula may be the same or different. Each
of R.sup.27 to R.sup.41 may be the same or different. For instance,
all of R.sup.27 and R.sup.28 may be the same or different, and all
of R.sup.35 and R.sup.36 may be the same or different.
[0169] Letter symbol n in the general formulae (XXI) to (XXVII) is
within the range of 0 to 10. When it is more than 10, the component
(B) has a high melt viscosity and hence the curing resin
composition also has a high viscosity at the time of its melt
molding, tending to cause faulty filling and deformation of bonding
wires (i.e., gold wires which connect device components with
leads). It is preferable that the average n in one molecule is set
within the range of 0 to 4. The values of i, j, k, q in the general
formulae (XXI) to (XXVII) are independent for each number of each
R.
[0170] When the epoxy resin (C) is used as the curing resin (B) and
the phenolic resin is used as the curing agent (D) of the epoxy
resin in the invention, the mixing proportion of the component (C)
and the component (D) is preferably set within the range of 0.5 to
2.0, more preferably 0.7 to 1.5, and still more preferably 0.8 to
1.3 in the proportion (the number of the hydroxyl groups in the
phenolic resin/the number of the epoxy groups in the epoxy resin)
of hydroxyl group equivalent weight of the all phenolic resin based
on the epoxy equivalent weight of all epoxy resins. If it is less
than 0.5, the epoxy resin may cure insufficiently to tend to make
cured products have poor heat resistance, moisture resistance and
electrical properties. If on the other hand it is more than 2.0,
the phenolic resin component is so excessive that curing may be
insufficient and phenolic hydroxyl groups may remain in the cured
resin in a large quantity, tending to result in poor electrical
properties and moisture resistance.
[0171] More than one kind of a general curing accelerator for
accelerating the curing reaction of curing resin can be used in
combination besides the curing accelerator component (A) for the
curing resin composition of the invention. Examples of the curing
accelerators used in combination include a cycloamidine compound
such as diazabicycloalkene such as 1,5-diazabicyclo[4.3.0]nonene-5
and 1,8-diazabicyclo[5.4.0]undecene-7, derivatives thereof, phenol
novolak salts thereof, a compound which has intramolecular
polarisation obtained by addition of these compounds to compounds
having 7C bonds such as a maleic anhydride, quinone compounds such
as 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone,
2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone,
2,3-dimethoxy-5-methyl-1,4-benzoquinone,
2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone
anddiazophenylmethane; tertiary amines such as triethylenediamine,
benzildimethylamine, triethanolamine, dimethylaminoethanol and
tris(dimethylaminomethyl)phenol, derivatives thereof; imidazoles
such as 2-methylimidazole, 2-phenylimidazole,
2-phenyl-4-methylimidazole and 2-heptadecylimidazole;
tetra-substituted-phosphonium tetra-substituted borates such as
tetra phenylphosphonium tetra phenyl borate; tetra phenylboron
salts such as 2-ethyl-4-methylimidazole tetra phenyl borate and
N-methylimorpholine tetra phenyl borate; organophosphines such as
triphenylphosphine, diphenyl(p-tolyl)phosphine,
tris(alkylphenyl)phosphines, tris(alkoxyphenyl)phosphines,
tris(alkylalkoxyphenyl)phosphines, tris(dialkylphenyl)phosphines,
tris(trialkylphenyl)phosphines, tris(tetraalkylphenyl)phosphines,
tris(dialkoxyphenyl)phosphines, tris(trialkoxypheny)phosphines,
tris(tetraalkoxyphenyl)phosphines, trialkyl phosphines, dialkylaryl
phosphines, alkyldiaryl phosphines; or complexes of any of these
organophosphines with organoborons; a compound which has
intramolecular polarisation obtained by addition of these
organophosphines to compounds having .pi. bonds such as a maleic
anhydride, quinone compound such as 1,4-benzoquinone,
2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone,
2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone,
2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone and
diazophenylmethane.
[0172] When any of these curing accelerators are used in
combination, the component (A) may preferably be mixed in an amount
not less than 30% by weight, and more preferably not less than 50%
by weight, based on the total weight of the curing accelerator. The
component (A) mixed in an amount less than 30% by weight tends to
reduce curability and/or flow properties under moisture absorption,
and thereby the effect of the present invention tends to be less
effective.
[0173] On the total weight of the curing accelerators inclusive of
the component (A), there are no particular limitations as long as
these are mixed in an amount necessary for achieving the curing
acceleration effect. From the viewpoint of curability under
moisture absorption and flow properties, the weight of 0.1 to 10
part by weight is preferable based on 100 parts by weight of the
total weight of the curing resin (B), and more preferably 1 to 7.0
part by weight. If these are in an amount less than 0.1 part by
weight, the curing may be difficult in a short time, and, in an
amount more than 10 parts by weight, the curing rate may be too
high to obtain good molded products.
[0174] The curing resin composition of the invention may optionally
be incorporated with inorganic filler (E). Especially when the
curing resin composition is used as the encapsulation molding
material, it is preferable for the molding material to contain the
inorganic filler (E). There are no particular limitations on the
inorganic filler (E) which is used in the invention and is
generally used for the encapsulation molding material. The
inorganic filler (E) may include fine powders of fusedsilica,
crystal silica, glass, alumina, calcium carbonate, zirconium
silicate, calcium silicate, silicon nitride, aluminum nitride,
boron nitride, beryllia, zirconia, zircon, forsterite, steatite,
spinel, mullite, titania, talc, clay and mica, or sphered beads of
any of these. Also, as inorganic filler having a flame-retardant
effect, it may include aluminum hydroxide, magnesium hydroxide, a
complex metal hydroxide such as a complex hydroxide of magnesium
and zinc, and zinc borate. Of the foregoing inorganic fillers,
fused silica is preferred from the viewpoint of lowering the
coefficient of linear expansion, and alumina from the viewpoint of
a high thermal conductivity. Any of these may be used alone or in
combination of two or more.
[0175] There are no particular limitations on the amount of mixing
of the inorganic filler (E) as long as the effect of the invention
can be achieved. It may preferably be mixed in an amount ranging
from 70 to 95% by weight based on the weight of the curing resin
composition. Since the inorganic filler is added for the purpose of
improving the coefficient of linear expansion, thermal
conductivity, modulus of elasticity or the like of cured products,
its mixing in an amount less than 70% by weight tend to not bring
about any sufficient improvement of these properties, and, in an
amount more than 95% by volume, the curing resin composition may
have a very high viscosity to have low flow properties, tending to
make it difficult to carry out molding.
[0176] The inorganic filler (E) may also preferably have an average
particle diameter ranging from 1 to 50 .mu.m, and particularly
preferably from 10 to 30 .mu.m. If it has an average particle
diameter smaller than 1 .mu.m, the resin composition tends to
increase in viscosity. If it has an average particle diameter
larger than 50 .mu.m, the resin component and the filler tend to
separate from each other, so that the cured product tends to be
non-uniformly formed or have varied properties and also any narrow
gaps in a mold tend to be low filled.
[0177] From the viewpoint of flow properties, the inorganic filler
(E) may preferably have a particle shape which is spherical rather
than rectangular, and may preferably have a particle size
distribution in a wide range. For example, when the filler is mixed
in an amount of 60% by weight or more, 70% by weight or more of the
particles may preferably be spherical and be size-distributed in a
wide range of from 0.1 to 80 .mu.m. Such filler can readily provide
a excellent fill structure, and hence may cause less increase in
viscosity of materials even when mixed in a large quantity, so that
compositions having superior flow properties can be obtained.
[0178] An anion exchanger can be optionally mixed with the curing
resin composition of the invention. When the curing resin
composition is used as the encapsulation molding material, it is
preferable to add an anion exchanger from the viewpoint of an
improvement in moisture resistance and high-temperature storage
characteristics of electronic component devices having device
components to be encapsulated. There are no particular limitations
on anion exchangers usable in the invention, and conventionally
known an ion exchangers can be used. For instance, Examples thereof
include hydrotalcites, and hydrated oxides of elements selected
from magnesium, aluminum, titanium, zirconium and bismuth. Any of
these may be used alone or in combination of any number of types.
In particular, hydrotalcite represented by the following general
formula (XXVIII) is preferable.
Mg.sub.1-xAl.sub.x(OH).sub.2(CO.sub.3).sub.X/2.H.sub.2O
(XXVIII)
[0179] (0<X.ltoreq.0.5, m is a positive number.)
[0180] There are no particular limitations on the amount of any of
these anion exchangers to be mixed, as long as it is an amount
sufficient for capturing the anions such as halide ions. It may
preferably be set in the range of from 0.1 to 30% by weight, and
more preferably from 1 to 5% by weight, based on the curing resin
(B).
[0181] Known colorants such as carbon black, organic dyes, organic
pigments, titanium oxide, red lead and red iron oxide may be
optionally mixed for the curing resin composition of the
invention.
[0182] The curing resin composition of the invention may be
incorporated with a release agent for providing a good
releasability to a mold at the time of molding. There are no
particular limitations on the release agents used in the invention,
and the conventionally known release agents can be used. Examples
of the release agents include higher fatty acids such as carnauba
wax, montanic acid and stearic acid, higher fatty acid metal salts,
an ester type wax such as montanate, polyolfin type wax such as
oxidation polyethylene and non-oxidatlon polyethylene. These may be
used alone or in combination of two or more. In particular, as the
release agent, the oxide type or non-oxide type polyolefin wax may
preferably be added in an amount of from 0.01 to 10% by weight, and
more preferably from 0.1 to 5% by weight of the curing resin (B).
If it is in an amount less than 0.01% by weight, sufficient
releasability tends to be not obtainable. If it is in an amount
more than 10% by weight, there is a possibility of deteriorating
adhesion. The polyolefin wax may include low-molecular-weight
polyethylene having number-average molecular weight of about 500 to
about 10,000, such as H4, PE or PED series available from Hoechst
Corp. as marketed commodity. When any of these additional release
agent is used in combination in addition to the polyolefin wax, it
may preferably be mixed in a proportion of from 0.1 to 10% by
weight, and more preferably from 0.5 to 3% by weight, based on the
curing resin (B).
[0183] The curing resin composition of the invention may be
optionally incorporated with a flame retardant for imparting flame
retardance. There are no particular limitations on the flame
retardant used in the invention. As the flame retardant, usable are
known organic or inorganic compounds containing a halogen atom, an
antimony atom, a nitrogen atom or a phosphorus atom, metal
hydroxides and acenaphthylene. These may be used alone or in
combination of two or more types. There are no particular
limitations on the amount of mixing of the flame retardant as long
as the flame-retardant effect can be achieved. The flame retardant
may preferably be mixed in a proportion of from 1 to 30% by weight,
and more preferably from 2 to 15% by weight, based on the epoxy
resin (C).
[0184] Known coupling agents for improving adhesion between the
resin component and the filler can be added to the encapsulation
curing resin composition of the invention. The known coupling
agents including silane compounds such as epoxysilane,
mercaptosilane, aminosilane, alkylsilane, ureidosilane and
vinylsilane, titanium compounds, aluminum chelates, and
aluminum/zirconium compounds or the like can e used.
[0185] It is preferable that the amount of mixing of the coupling
agent is 0.05 to 5 percent by weight based on the inorganic filler
(E), and more preferably 0.1 to 2.5 percent by weight. When the
amount of mixing is less than 0.05 percent by weight, adhesion with
the flame tends to reduce. When the amount of mixing is more than 5
percent by weight, the molding properties of the package tends to
reduce.
[0186] Examples of the coupling agents include, for instance,
silane coupling agents such as vinyltrichlorosilane,
vinyltriethoxysilane, vinyltris(.beta.-methoxyethoxy)silane,
.gamma.-methacryloxypropyltrimetho- xysilane,
.gamma.-methacryloxypropyltriethoxysilane,
.gamma.-acryloxypropyltrimethoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyl- trimethoxysilane,
.gamma.-glycidoxypropyltrimethoxysilane,
.gamma.-glycidoxypropylmethyldimethoxysilane,
vinyltriacetoxysilane, .gamma.-mercaptopropyltrimethoxysilane,
.gamma.-aminopropyltriethoxysilan- e,
.gamma.-anilinopropyltrimethoxysilane,
.gamma.-anilinopropyltriethoxysi- lane,
.gamma.-anilinopropylmethyldimethoxysilane,
.gamma.-anilinopropylmet- hyldiethoxysilane,
.gamma.-anilinopropylethyldiethoxysilane,
.gamma.-anilinopropylethyldimethoxysilane,
.gamma.-anilinomethyltrimethox- ysilane,
.gamma.-anilinomethyltriethoxysilane, .gamma.-anilinomethylmethyl-
dimethoxysilane, .gamma.-anilinomethylmethyldiethoxysilane,
.gamma.-anilinomethylethyldiethoxysilane,
.gamma.-anilinomethylethyldimet- hoxysilane,
N-(p-methoxyphenyl)-.gamma.-aminopropyltrimethoxysilane,
N-(p-methoxyphenyl)-.gamma.-aminopropyltriethoxysilane,
N-(p-methoxyphenyl)-.gamma.-aminopropylmethyldimethoxysilane,
N-(p-methoxyphenyl)-.gamma.-aminopropylmethydiethoxysilane,
N-(p-methoxyphenyl)-.gamma.-aminopropylethyldiethoxysilane,
N-(p-methoxyphenyl)-.gamma.-aminopropylethyldimethoxysilane,
.gamma.-(N-methyl)aminopropyltrimethoxyslane,
.gamma.-(N-ethyl)aminopropy- ltrimethoxysilane,
.gamma.-(N-butyl)aminopropyltrimethoxysilane,
.gamma.-(N-benzyl)aminopropyltrimethoxysilane,
.gamma.-(N-methyl)aminopro- pyltriethoxysilane,
.gamma.-(N-ethyl)aminopropyltriethoxysilane,
.gamma.-(N-butyl)aminopropyltriethoxysilane,
.gamma.-(N-benzyl)aminopropy- ltriethoxysilane,
.gamma.-(N-methyl)aminopropylmethyldimethoxysilane,
.gamma.-(N-ethyl)aminopropylmethyldimethoxysilane,
.gamma.-(N-butyl)aminopropylmethyldimethoxysilane,
.gamma.-(N-benzyl)aminopropylmethyldlmethoxysilane,
.gamma.-(.beta.-aminoethyl)aminopropyltrimethoxysilane,
.gamma.-[bis(.beta.-hydroxyethyl)]aminopropyltriethoxysilane,
N-.beta.-(aminoethyl)-.gamma.-aminopropyltrimethoxysilane,
.gamma.-(.beta.-aminoethyl)aminopropyldimethoxymethylsilane,
N-(trimethoxysilylpropyl)ethylenediamine,
N-(dimethoxymethylsilylisopropy- l)ethylenediamine,
methyltrimethoxysilane, dimethyldimethoxysilane,
methyltriethoxysilane,
N-.beta.-(N-vinylbenzylaminoethyl)-.gamma.-aminopr-
opyltrimethoxysilane, .gamma.-chloropropyltrimethoxysilane,
hexamethyldisilane, vinyltrimethoxysilane and
.gamma.-mercaptopropylmethy- ldimethoxysilane, and titanate
coupling agents such as isopropyltriisostearoyltitanate,
isopropyltris(dioctylpyrophosphate)titan- ate,
isopropyltri(N-aminoethyl-aminoethyl)titanate,
tetraoctylbis(ditridesylphosphite)titanate,
tetra(2,2-diallyloxymethyl-1-- butyl)bis(ditridesyl)phosphate
titanate, bis(dioctylpyrophosphate)oxyaceta- te titanate,
bis(dioctylpyrophosphate)ethylenetitanate,
isopropyltrioctanoyltitanate,
isopropyldimethacrylisostearoyltitanate,
isopropyltridodecylbenzenesulfonyltitanate,
isopropylisostearoyldiacrylti- tanate,
isopropyltri(dioctylphosphate)titanate, isopropyltricumylphenyltit-
anate and tetraisopropylbis(dioctylphosphite)titanate. The coupling
agents are not limited thereto. These may be used alone or in
combination of two or more types. In these, the coupling agent
having a secondary amino group is preferable from the viewpoint of
the flow properties and the wire flow.
[0187] A stress relaxation agent such as silicone oil and silicone
rubber powder can be optionally mixed to the curing resin
composition of the invention. Mixing the stress relaxation agent
can reduce the amount of the warp transformation of the package and
the package crack. There are no particular limitations on the
stress relaxation agents which can be used as long as the stress
relaxation agents are a known plasticizer (stress relaxation agent)
which is generally used. Examples of the plasticizers generally
used include thermoplastic elastomers of silicone type, styrene
type, olefine type, urethane type, polyester type, polyether type,
polyamide type, polybutadiene type; rubber particles such as NR
(crude rubber), NBR (acrylonitrile-butadiene rubber), an acrylic
rubber, a urethane rubber and a silicone powder; and rubber
particles having a core shell structure such as
methylmethacrylate-styrene-butadien- e copolymer (MBS),
methylmethacrylate-silicone copolymer and
methylmethacrylate-butylacrylate copolymer. These may be used alone
or in combination of two or more types. In particularly, the
silicone type plasticizer is preferable, and examples of the
silicone type plasticizer including a plasticizer having an epoxy
group, a plasticizer having an amino group, and a
polyether-modified plasticizer of these.
[0188] Incidentally, the curing resin composition of the invention
may be prepared by any methods as long as the materials of various
types can uniformly be dispersed and be mixed. A commonly available
preparation method may include a method in which materials
formulated in prescribed quantities are thoroughly mixed by means
of a mixer and the mixture obtained is melt-kneaded by means of a
mixing roll or an extruder, followed by cooling and then
pulverization. For example, it can be obtained by stirring and
mixing the above components uniformly in prescribed quantities and
kneading the resultant mixture by means of a kneader, roll mill or
extruder previously heated to 70 to 140.degree. C. followed by
cooling and then pulverization. The product obtained may be made
into tablets in such a size and weight that may suit to molding
conditions, so as to be usable with ease.
[0189] The electronic component device of the present invention can
be produced by mounting active devices such as semiconductor chips,
transistors, diodes or thyristors and passive devices such as
capacitors, resistors or coils on a support member such as a lead
frame, a tape carrier having been wired, a wiring board, glass or a
silicon wafer, and encapsulating necessary portions with the curing
resin composition of the present invention. Such electronic
component devices include commonly available resin-encapsulated ICs
in which semiconductor devices are fastened onto a lead frame, and
terminals (such as bonding pads) and leads of the device are
connected by wire bonding or through bumps, followed by
encapsulation with the curing resin composition of the invention by
transfer molding or the like. The commonly available
resin-encapsulated ICs include DIP (dual-inline package), PLCC
(plastic-leaded chip carrier), QFP (quad flat package), SOP (small
outline package), SOJ (small outline J-lead package), TSOP (thin
small outline package) and TQFP (thin quad flat package). The
electronic component devices include TCPs (tape carrier packages)
in which semiconductor chips bonded to a tape carrier through bumps
are encapsulated with the curing resin composition of the
invention; COB (chip on board) modules in which active devices such
as semiconductor chips, transistors, diodes or thyristors and/or
passive devices such as capacitors, resistors or coils which are
connected to wirings formed on a wiring board and a glass by using
wire bonding, flip chip bonding and solder or the like are
encapsulated with the curing resin composition of the invention;
hybrids IC; multichip modules; BGAs (ball grid arrays) in which
devices are mounted on an organic substrate on the back of which
terminals for wiring-board connection have been formed, and the
devices are connected through bumps or by wire bonding, to wirings
formed on the organic substrate, followed by encapsulation with the
curing resin composition of the invention; CSPs (chip size
packages) or the like. The curing resin composition of the
invention is also effectively usable in printed circuit boards.
[0190] As methods of encapsulation for the electronic component
device by using the curing resin composition of the invention,
low-pressure transfer molding is most commonly used. Injection
molding or compression molding may also be used.
EXAMPLES
[0191] Examples of the invention will be described below. The
examples of the present invention are not intended as a definition
of the limits of the invention.
Synthesis Example For a Curing Accelerator For a Curing Resin]
Synthesis Example 1
[0192] Triphenylphosphine of 20.4 g, 4-bromo phenol of 26.9 g,
nickel (II) chloride hexahydrate of 3.5 g and DMF of 20 g were put
in a flask, and were stirred at 145.degree. C. for 6 hours. Under
reduced pressure, the reaction liquid was concentrated, and
methanol of 60 ml was added to the reaction liquid. Sodium
hydroxide of 9.3 g was then added to the reaction liquid, and the
reaction liquid was stirred until the sodium hydroxide was
completely dissolved.
[0193] The solution obtained was filtered on celite, and was
concentrated under reduced pressure until the whole amount became
about 50 ml. The solution was then turned on into water of 1 liter,
and the crystal deposited was filtered. The crystal was then dried
under reduced pressure after washing, and a compound of 25.6 g was
obtained. Elementary analysis revealed that C was 81.34 and H was
5.40 as calculated values (%), and C was 81.21 and H was 5.34 as
measured values (%).
Synthesis Example 2
[0194] A compound of 24.5 g was obtained in the same manner as in
Synthesis Example 1 except that 4-chlorophenol of 20 g was put in
place of 4-bromo phenol. Elementary analysis revealed that C was
81.34 and H was 5.40 as calculated values (%), and C was 81.23 and
H was 5.33 as measured values (%).
Synthesis Example 3
[0195] Triphenylphosphine of 20.4 g, 3-bromo phenol of 26.9 g,
nickel (II) chloride hexahydrate of 3.5 g and DMF of 20 g were put
in a flask, and were stirred at 145.degree. C. for 6 hours. Under
reduced pressure, the reaction liquid was concentrated, and
methanol of 60 ml was added to the reaction liquid. Sodium
hydroxide of 9.3 g was then added to the reaction liquid, and the
reaction liquid was stirred until the sodium hydroxide was
completely dissolved. The solution obtained was filtered on celite,
and was concentrated under reduced pressure until the whole amount
became about 50 ml. The solution was then turned on into water of 1
liter. The resultant solution was concentrated until the resultant
solution become about 200 ml, and the crystal deposited was
filtered. The crystal was then dried, and a compound of 10.2 g was
obtained. Elementary analysis revealed that C was 81.34 and H was
5.40 as calculated values (%), and C was 81.15 and H was 5.29 as
measured values (%).
Synthesis Example 4
[0196] A compound of 24.3 g was obtained in the same manner as in
Synthesis Example 1 except that 2-bromophenol of 26.9 g was put in
place of 4-bromophenol. Elementary analysis revealed that C was
81.34 and H was 5.40 as calculated values (%), and C was 81.22 and
H was 5.32 as measured values (%).
Synthesis Example 5
[0197] A compound of 25.2 g was obtained in the same manner as in
Synthesis Example 1 except that 2-chlorophenol of 20 g was put in
place of 4-bromophenol. Elementary analysis revealed that C was
81.34 and H was 5.40 as calculated values (%), and C was 81.20 and
H was 5.34 as measured values (%).
Synthesis Example 6
[0198] A compound of 25.9 g was obtained in the same manner as in
Synthesis Example 1 except that 4-bromo-2,6-dimethylphenol of 31.3
g was put in place of 4-bromophenol. Elementary analysis revealed
that C was 81.66 and H was 6.06 as calculated values (%), and C was
81.47 and H was 5.99 as measured values (%).
Synthesis Example 7
[0199] A compound of 27.2 g was obtained in the same manner as in
Synthesis Example 2 except that tri-p-tolylphosphine of 23.7 g was
put in place of triphenylphosphine. Elementary analysis revealed
that C was 81.80 and H was 6.36 as calculated values (%), and C was
81.67 and H was 6.29 as measured values (%).
Synthesis Example 8
[0200] A compound of 25.9 g was obtained in the same manner as in
Synthesis Example 1 except that 6-bromo-2-naphthol of 36.2 g was
put in place of 4-bromophenol. Elementary analysis revealed that C
was 83.15 and H was 5.23 as calculated values (%), and C was 83.01
and H was 5.18 as measured values (%).
Synthesis Example 9
[0201] A compound of 16.5 g was obtained in the same manner as in
Synthesis Example 2 except that cyclohexyldiphenylphosphine of 20.9
g was put in place of triphenylphosphine. Elementary analysis
revealed that C was 79.98 and H was 6.99 as calculated values (%),
and C was 79.86 and H was 6.90 as measured values (%)
[0202] The compounds obtained by the Synthesis Examples 1 to 9 were
analyzed by the following method.
[0203] (1) .sup.1H-NMR
[0204] The compound of about 10 mg was solved in methanol-d4 of
about 0.5 ml, and the resultant solution was put in a sample tube
of .phi.5 mm. The solution was measured by AC-250 (trade name:
manufactured by Bruker Japan Co., Ltd). The shift value was based
on a small amount of CHD.sub.2OH (3.3 ppm) contained in the
solvent.
[0205] (2) .sup.13C-NMR
[0206] The compound of about 100 mg was solved in methanol-d4 of
about 0.5 ml, and the resultant solution was put in a sample tube
of .phi.5 mm. The solution was measured by AC-250 (trade name:
manufactured by Bruker Japan Co., Ltd). The shift value was based
on methanol-d4 (49ppm).
[0207] (3) .sup.31P-NMR
[0208] The compound of about 100 mg was solved in methanol-d4 of
about 0.5 ml, and the resultant solution was put in a sample tube
of .phi.5 mm. The solution was measured by AC-250 (trade name,
manufactured by Bruker Japan Co., Ltd). The shift value was based
on triphenyl phosphate (0 ppm).
[0209] (4) IR
[0210] The compound was measured by KBr method using FTS 3000MX
(trade name, manufactured by Bio-Rad Laboratories).
[0211] From these results of analysis, the compounds synthesized by
the Synthesis Examples 1 and 2 were the same compound (compound 1),
and it was ascertained that the structures thereof were represented
by the following formula (XXIX). The yields thereof were 93%
and89%. The spectrums of .sup.1H-NMR(CD.sub.3OD),
.sup.13C-NMR(CD.sub.3OD) .sup.31P-NNR(CD.sub.3OD) and IR (KBr
method) of the compound 1 were respectively represented in FIGS. 1,
2, 3, 4.
[0212] From these results of analysis, it was ascertained that the
structure of the compound (compound 2) synthesized by the Synthesis
Example 3 was represented by the following formula (XXX). The yield
was 37%. The spectrums of .sup.1H-NMR(CD.sub.3OD),
.sup.13C-NMR(CD30D), .sup.31P-NMR(CD.sub.3OD) and IR (KBr) of the
compound 2 were respectively represented in FIGS. 5, 6, 7, 8.
[0213] From these results of analysis, the compounds synthesized by
the Synthesis Examples 4 and 5 were the same compound (compound 3),
and it was ascertained that the structures thereof were represented
by the following formula (XXXI). The yields thereof were
respectively 88% and 91%. The spectrums of .sup.1H-NMR(CD.sub.3OD),
.sup.13C-NMR(CD.sub.3OD), .sup.31P-NMR(CD.sub.3OD) and IR (KBr)
were respectively represented in FIGS. 9, 10, 11, 12.
[0214] From these results of analysis, it was ascertained that the
structure of the compound (compound 4) synthesized by the Synthesis
Example 6 was represented by the following formula (XXXII). The
yield was 87%. The spectrums of .sup.1H-NMR(CD.sub.3OD),
.sup.13C-NMR(CD.sub.3OD), .sup.31P-NMR(CD.sub.3OD) and IR (KBr)
were respectively represented in FIGS. 13, 14, 15, 16.
[0215] From these results of analysis, it was ascertained that the
structure of the compound (compound 5) synthesized by the Synthesis
Example 7 was represented by the following formula (XXXIII). The
yield was 88%. The spectrums of .sup.1H-NMR(CD.sub.3OD),
.sup.13C-NMR(CD.sub.3OD), .sup.31P-NNR(CD.sub.3OD) and IR (KBr)
were respectively represented in FIGS. 17, 18, 19, 20.
[0216] From these results of analysis, it was ascertained that the
structure of the compound (compound 6) synthesized by the Synthesis
Example 8 was represented by the following formula (XXXIV). The
yield was 82%. The spectrums of .sup.1H-NMR(CD.sub.3OD),
.sup.13C-NMR(CD.sub.3OD), .sup.31P-NMR(CD.sub.3OD) and IR (KBr)
were respectively represented in FIGS. 21, 22, 23, 24.
[0217] From these results of analysis, it was ascertained that the
structure of the compound (compound 7) synthesized by the Synthesis
Example 9 was represented by the following formula (XXXV). The
yield was 59%. The spectrums of .sup.1H-NMR(CD.sub.3OD),
.sup.13C-NMR(CD.sub.3OD), .sup.31P-NMR(CD.sub.3OD) and IR (KBr)
were respectively represented in FIGS. 25, 26, 27, 28. 24
[0218] The compounds other than the compound (XXX) can be
represented by the resonance of the formula (IV) among the
compounds (XXIX) to (XXXV), and the compound (XXX) cannot be
represented by the resonance of the formula (IV).
[0219] (Preparation and Property Evaluation of Curing Resin
Composition)
Examples 1 to 61 and Comparative Examples 1 to 81
[0220] As the epoxy resin, prepared were a biphenyl type epoxy
resin having an epoxy equivalent weight of 196 and a melting point
of 106.degree. C. (epoxy resin 1: YX-4000H (tradename);
manufactured by Japan Epoxy Resins Co., Ltd),
[0221] a sulfur atom content type epoxy resin having an epoxy
equivalent weight of 245 and a melting point of 110.degree. C.
(epoxy resin 2: YSLV-120TE (trade name); manufactured by Nippon
Steel Chemical Co., Ltd.),
[0222] a diphenylmethane skeleton type epoxy resin having an epoxy
equivalent weight of 192 and a melting point of 79.degree. C.
(epoxy resin 3: YSLV-80XY (trade name); manufactured by Nippon
Steel Chemical Co., Ltd.),
[0223] a stilbene type epoxy resin having an epoxy equivalent
weight of 210 and a melting point of 120.degree. C. (epoxy resin 4:
ESLV-210 (trade name); manufactured by Sumitomo Chemical Co.,
Ltd.),
[0224] an o-cresol novolak type epoxy resin having an epoxy
equivalent weight of 195 and a softening point of 62.degree. C.
(epoxy resin 5: ESCN-190-2 (trade name); manufactured by Sumitomo
Chemical Co., Ltd.),
[0225] a dicyclopentadiene modified phenol novolac type epoxy resin
having an epoxy equivalent weight of 264 and a softening point of
64.degree. C. (epoxy resin 6: HP-7200 (trade name) manufactured by
Dainippon Ink and Chemicals, Incorporated),
[0226] a salicylaldehyde type epoxy resin having an epoxy
equivalent weight of 167 (epoxy resin 7: EPPN-502H (trade name)
manufactured by Nippon Kayaku Co., Ltd.),
[0227] a mixture (epoxy resin 8: CER-3000 (trade name) manufactured
by Nippon Kayaku Co., Ltd.) of an epoxidized material of an aralkyl
type phenolic resin and a biphenyl type epoxy resin in a ratio of
80/20 by weight, having an epoxy equivalent weight of 242 and a
softening point of 95.degree. C. and
[0228] an epoxidized material of aralkyl type phenolic resin having
an epoxy equivalent weight of 265 and a softening point of
66.degree. C. (epoxy resin 9: ESN-175 (tradename) Nippon Steel
Chemical Co., Ltd.).
[0229] A brominated bisphenol-A epoxy resin having an epoxy
equivalent weight of 393, a softening point 80.degree. C. and a
bromine content of 48% by weight (brominated epoxy resin) was
prepared as an epoxy resin having a flame-retardant effect.
[0230] As the curing agent, prepared were a phenol aralkyl resin
having a hydroxyl group equivalent weight of 176 and a softening
point of 70.degree. C. (curing agent 1: MILEX XL-225 (trade name),
manufactured by Mitsui Chemicals Inc.),
[0231] a biphenyl skeleton type phenolic resin having a hydroxyl
group equivalent weight of 199 and a softening point 89.degree. C.
(curing agent 2: MEH-7851 (trade name) manufactured by Meiwa
Plastic Industries, Ltd.),
[0232] a naphthol aralkyl resin having a hydroxyl group equivalent
weight of 183 and softening point 79.degree. C. (Curing agent 3:
SN-170 (trade name), manufactured by Nippon Steel Chemical Co.,
Ltd.),
[0233] a dicyclopentadiene modified phenol novolac resin having a
hydroxyl group equivalent weight of 170 and a softening point of
93.degree. C. (curing agent 4: DPP (trade name), manufactured by
Nippon Petrochemicals Co., Ltd.),
[0234] a phenol novolac resin having a hydroxyl group equivalent
weight of 106 (curing agent 5: HP-850N (trade name), manufactured
by Hitachi Chemical Co., Ltd.),
[0235] a copolymer type phenolic resin of a benzaldehyde type
phenolic resin and an aralkyl type phenolic resin having a hydroxyl
group equivalent weight of 156 (curing agent 6: HE-510 (trade
name), manufactured by Sumikin Chemical Co., Ltd.), and
[0236] a salicylaldehyde type phenolic resin having a hydroxyl
group equivalent weight of 106 (curing agent 7: MEH-7500 (trade
name) manufactured by Meiwa Plastic Industries, Ltd.).
[0237] A resin (curing agent 8: SN-170AR10 (trade name)
manufactured by Nippon Steel Chemical Co., Ltd.) obtained by adding
acenaphthylene of 10 percent by weight to a naphthol aralkyl resin
having a hydroxyl group equivalent weight of 209 and a softening
point 73.degree. C. was prepared as a phenolic resin having a
flame-retardant effect.
[0238] As the curing accelerators of Examples, prepared were the
compound 1 (curing accelerator 1), the compound 2 (curing
accelerator 2), the compound 3 (curing accelerator 3), the compound
4 (curing accelerator 4), the compound 5 (curing accelerator 5),
the compound 6 (curing accelerator 6), the compound 7 (curing
accelerator 7). As the curing accelerators of Comparative Examples,
prepared were triphenylphosphine (curing accelerator A), an
addition product (curing accelerator B) of triphenylphosphine and
1,4-benzoquinone, an addition product (curing accelerator C) of
tri-n-butylphosphine and 1,4-benzoquinone, an addition product
(curing accelerator D) of tricyclohexylphosphine and
1,4-benzoquinone, (cyclopentadienilidene) triphenylphosphorane
(curing accelerator E) represented by the following formula
(XXXVI), 2-(triphenylphosphaaniliden) succinicanhydride (curing
accelerator F) represented by the following formula (XXXVII), a
phenol novolac salt (curing accelerator G: SA-841(trade name)
manufactured by San-Apro Ltd.) of DBU 25
[0239] Spherical molten silica having an average grain diameter of
17.5 .mu.m and a specific surface of 3.8 m.sup.2/g is used as the
inorganic filler. As the other additive ingredients, prepared were
epoxysilane (.gamma.-glycidoxypropyltrimethoxysilane) as a coupling
agent, carbon black (MA-100; trade name, manufactured by Mitsubishi
Chemical Co., Ltd.) as the colorant, carnauba wax (Serarika NODA
Co., Ltd.) as the release agent, and antimony trioxide as the flame
retardant.
[0240] Curing resin compositions of Examples 1 to 61 and
Comparative Examples 1 to 81 were obtained by mixing in the weight
part represented in tables 1 to 13 using these, and roll-kneading
under conditions of the kneading temperature of 80.degree. C. and
kneading time of 15 minutes.
1TABLE 1 comparative mixing example example material 1 2 3 4 5 6 7
1 2 3 4 5 6 7 epoxy resin 1 85 85 85 85 85 85 85 85 85 85 85 85 85
85 brominated 15 15 15 15 15 15 15 15 15 15 15 15 15 15 epoxy resin
curing 83 83 83 83 83 83 83 83 83 83 83 83 83 83 agent 1 curing 2.3
accelerator 1 curing 2.9 accelerator 2 curing 2.3 accelerator 3
curing 2.5 accelerator 4 curing 2.6 accelerator 5 curing 3.0
accelerator 6 curing 3.1 accelerator 7 curing 2.4 accelerator A
curing 3.4 accelerator B curing 2.8 accelerator C curing 3.5
accelerator D curing 3.0 accelerator E curing 3.3 accelerator F
curing 9.0 accelerator G carnauba wax 1 1 1 1 1 1 1 1 1 1 1 1 1 1
antimony 6 6 6 6 6 6 6 6 6 6 6 6 6 6 trioxide carbon black 2.6 2.6
2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 epoxy silane 11 11
11 11 11 11 11 11 11 11 11 11 11 11 molten silica 1510 1515 1510
1512 1512 1515 1516 1511 1518 1514 1519 1515 1518 1559 molten
silica 88 88 88 88 88 88 88 88 88 88 88 88 88 88 (% by weight)
[0241]
2TABLE 2 comparative mixing example example material 8 9 10 11 12
13 14 8 9 10 11 12 13 14 epoxy 85 85 85 85 85 85 85 85 85 85 85 85
85 85 resin 2 brominated 15 15 15 15 15 15 15 15 15 15 15 15 15 15
epoxy resin curing 68 68 68 68 68 68 68 68 68 68 68 68 68 68 agent
1 curing 2.3 accelerator 1 curing 2.9 accelerator 2 curing 2.3
accelerator 3 curing 2.5 accelerator 4 curing 2.6 accelerator 5
curing 3.0 accelerator 6 curing 3.1 accelerator 7 curing 2.4
accelerator A curing 3.4 accelerator B curing 2.8 accelerator C
curing 3.5 accelerator D curing 3.0 accelerator E curing 3.3
accelerator F curing 9.0 accelerator G carnauba wax 1 1 1 1 1 1 1 1
1 1 1 1 1 1 antimony 6 6 6 6 6 6 6 6 6 6 6 6 6 6 trioxide carbon
black 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 epoxy
silane 11 11 11 11 11 11 11 11 11 11 11 11 11 11 molten silica 1398
1403 1398 1400 1401 1403 1404 1399 1406 1402 1407 1403 1406 1447
molten silica 88 88 88 88 88 88 88 88 88 88 88 88 88 88 (% by
weight)
[0242]
3TABLE 3 comparative mixing example example material 15 16 17 18 19
20 21 15 16 17 18 19 20 21 epoxy 85 85 85 85 85 85 85 85 85 85 85
85 85 85 resin 3 brominated 15 15 15 15 15 15 15 15 15 15 15 15 15
15 epoxy resin curing 96 96 96 96 96 96 96 96 96 96 96 96 96 96
agent 2 curing 3.0 accelerator 1 curing 3.8 accelerator 2 curing
3.0 accelerator 3 curing 3.3 accelerator 4 curing 3.4 accelerator 5
curing 3.9 accelerator 6 curing 4.0 accelerator 7 curing 3.1
accelerator A curing 4.4 accelerator B curing 3.6 accelerator C
curing 4.6 accelerator D curing 3.9 accelerator E curing 4.3
accelerator F curing 11.7 accelerator G carnauba wax 1 1 1 1 1 1 1
1 1 1 1 1 1 1 antimony 6 6 6 6 6 6 6 6 6 6 6 6 6 6 trioxide carbon
black 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 epoxy
silane 11 11 11 11 11 11 11 11 11 11 11 11 11 11 molten silica 1608
1614 1608 1610 1611 1615 1616 1609 1619 1613 1620 1615 1618 1672
molten silica 88 88 88 88 88 88 88 88 88 88 88 88 88 88 (% by
weight)
[0243]
4TABLE 4 comparative comparative mixing example example example
example material 22 23 22 23 24 24 25 25 26 27 epoxy 85 85 85 85 85
resin 1 epoxy 85 85 85 85 85 resin 4 brominated 15 15 15 15 15 15
15 15 15 15 epoxy resin curing 78 78 78 78 78 agent 1 curing 94 94
94 94 94 agent 2 curing 2.1 2.8 accelerator 1 curing 2.1 2.8
accelerator 3 curing 2.2 2.9 accelerator A curing 3.1 4.1
accelerator B curing 2.5 3.4 accelerator C carnauba 1 1 1 1 1 1 1 1
1 1 wax antimony 6 6 6 6 6 6 6 6 6 6 trioxide carbon 2.6 2.6 2.6
2.6 2.6 2.6 2.6 2.6 2.6 2.6 black epoxy 11 11 11 11 11 11 11 11 11
11 silane molten 1471 1471 1472 1479 1475 1593 1593 1594 1603 1598
silica molten silica 88 88 88 88 88 88 88 88 88 88 (% by
weight)
[0244]
5TABLE 5 comparative comparative mixing example example example
example material 26 27 28 29 30 28 29 29 30 31 epoxy 85 85 85 85 85
85 85 85 85 85 resin 1 brominated 15 15 15 15 15 15 15 15 15 15
epoxy resin curing 86 86 86 86 86 agent 3 curing 50 50 50 50 50
agent 5 curing 2.5 2.1 accelerator 1 curing 2.5 2.1 accelerator 3
curing 2.6 2.2 accelerator A curing 3.7 3.1 accelerator B curing
3.1 2.5 accelerator C carnauba wax 1 1 1 1 1 1 1 1 1 1 antimony 6 6
6 6 6 6 6 6 6 6 trioxide carbon black 2.6 2.6 2.6 2.6 2.6 2.6 2.6
2.6 2.6 2.6 epoxy silane 11 11 11 11 11 11 11 11 11 11 molten
silica 1536 1536 1537 1545 1540 1266 1266 1267 1274 1270 molten
silica 88 88 88 88 88 88 88 88 88 88 (% by weight)
[0245]
6TABLE 6 comparative comparative mixing example example example
example material 30 31 34 35 36 32 33 37 38 39 epoxy 42.5 42.5 42.5
42.5 42.5 resin 1 epoxy 42.5 42.5 42.5 42.5 42.5 resin 2 epoxy 42.5
42.5 42.5 42.5 42.5 42.5 42.5 42.5 42.5 42.5 resin 5 brominated 15
15 15 15 15 15 15 15 15 15 epoxy resin curing 83 83 83 83 83 76 76
76 76 76 agent 1 curing 2.0 2.0 accelerator 1 curing 2.0 2.0
accelerator 3 curing 2.0 2.0 accelerator A curing 2.9 2.9
accelerator B curing 2.4 2.4 accelerator C carnauba wax 1 1 1 1 1 1
1 1 1 1 antimony 6 6 6 6 6 6 6 6 6 6 trioxide carbon black 2.6 2.6
2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 epoxy silane 11 11 11 11 11 11 11
11 11 11 molten silica 1264 1264 1265 1270 1267 1217 1217 1218 1223
1220 molten silica 86 86 86 86 86 86 86 86 86 86 (% by weight)
[0246]
7TABLE 7 comparative comparative mixing example example example
example material 34 35 40 41 42 36 37 43 44 45 epoxy 42.5 42.5 42.5
42.5 42.5 resin 4 epoxy 42.5 42.5 42.5 42.5 42.5 85 85 85 85 85
resin 5 brominated 15 15 15 15 15 15 15 15 15 15 epoxy resin curing
81 81 81 81 81 83 83 83 83 83 agent 1 curing 1.8 1.6 accelerator 1
curing 1.8 1.6 accelerator 3 curing 1.9 1.7 accelerator A curing
2.7 2.4 accelerator B curing 2.2 2.0 accelerator C carnauba wax 1 1
1 1 1 1 1 1 1 1 antimony 6 6 6 6 6 6 6 6 6 6 trioxide carbon black
2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 epoxy silane 11 11 11 11 11
11 11 11 11 11 molten silica 1248 1248 1248 1253 1250 1080 1080
1080 1084 1081 molten silica 86 86 86 86 86 84 84 84 84 84 (% by
weight)
[0247]
8TABLE 8 comparative comparative mixing example example example
example material 38 39 46 47 48 40 41 49 50 51 epoxy 85 85 85 85 85
85 85 85 85 85 resin 5 brominated 15 15 15 15 15 15 15 15 15 15
epoxy resin curing 81 81 81 81 81 agent 4 curing 50 50 50 50 50
agent 5 curing 1.8 1.4 accelerator 1 curing 1.8 1.4 accelerator 3
curing 1.9 1.4 accelerator A curing 2.7 2.0 accelerator B curing
2.2 1.7 accelerator C carnauba wax 1 1 1 1 1 1 1 1 1 1 antimony 6 6
6 6 6 6 6 6 6 6 trioxide carbon black 2.6 2.6 2.6 2.6 2.6 2.6 2.6
2.6 2.6 2.6 epoxy silane 11 11 11 11 11 11 11 11 11 11 molten
silica 1066 1066 1066 1071 1068 904 904 905 908 906 molten silica
84 84 84 84 84 84 84 84 84 84 (% by weight)
[0248]
9TABLE 9 comparative comparative mixing example example example
example material 42 43 52 53 54 44 45 55 56 57 epoxy 85 85 85 85 85
resin 5 epoxy 85 85 85 85 85 resin 6 brominated 15 15 15 15 15 15
15 15 15 15 epoxy resin curing 40 40 40 40 40 agent 4 curing 25 25
25 25 25 38 38 38 38 38 agent 5 curing 1.6 2.1 accelerator 1 curing
1.6 2.1 accelerator 3 curing 1.7 2.2 accelerator A curing 2.4 3.1
accelerator B curing 2.0 2.5 accelerator C carnauba wax 1 1 1 1 1 1
1 1 1 1 antimony 6 6 6 6 6 6 6 6 6 6 trioxide carbon black 2.6 2.6
2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 epoxy silane 11 11 11 11 11 11 11
11 11 11 molten silica 985 985 985 989 987 844 844 845 850 847
molten silica 84 84 84 84 84 84 84 84 84 84 (% by weight)
[0249]
10TABLE 10 comparative comparative mixing example example example
example material 46 47 58 59 60 48 49 61 62 63 epoxy 85 85 85 85 85
resin 1 epoxy 85 85 85 85 85 resin 3 brominated 15 15 15 15 15 15
15 15 15 15 epoxy resin curing 74 74 74 74 74 75 75 75 75 75 agent
6 curing 2.8 3.0 accelerator 1 curing 2.8 3.0 accelerator 3 curing
2.9 3.1 accelerator A curing 4.1 4.4 accelerator B curing 3.4 3.6
accelerator C carnauba wax 1 1 1 1 1 1 1 1 1 1 antimony 6 6 6 6 6 6
6 6 6 6 trioxide carbon black 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6
2.6 epoxy silane 11 11 11 11 11 11 11 11 11 11 molten silica 1444
1444 1445 1454 1449 1456 1456 1457 1467 1461 molten silica 88 88 88
88 88 88 88 88 88 88 (% by weight)
[0250]
11 TABLE 11 example comparative example example comparative example
mixing material 50 51 64 65 66 52 53 67 68 69 epoxy resin 1 85 85
85 85 85 epoxy resin 7 85 85 85 85 85 brominated 15 15 15 15 15 15
15 15 15 15 epoxy resin curing agent 7 50 50 50 50 50 58 58 58 58
58 curing 2.1 1.2 accelerator 1 curing 2.1 1.2 accelerator 3 curing
2.2 1.2 accelerator A curing 3.1 1.7 accelerator B curing 2.5 1.4
accelerator C carnauba wax 1 1 1 1 1 1 1 1 1 1 antimony 6 6 6 6 6 6
6 6 6 6 trioxide carbon black 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6
2.6 epoxy silane 11 11 11 11 11 11 11 11 11 11 molten silica 1266
1266 1267 1274 1270 944 944 944 947 945 molten silica 88 88 88 88
88 84 84 84 84 84 (% by weight)
[0251]
12 TABLE 12 example comparative example example comparative example
mixing material 54 55 70 71 72 56 57 73 74 75 epoxy resin 8 85 85
85 85 85 epoxy resin 9 85 85 85 85 85 brominated 15 15 15 15 15 15
15 15 15 15 epoxy resin curing agent 1 69 69 69 69 69 63 63 63 63
63 curing 1.8 1.8 accelerator 1 curing 1.8 1.8 accelerator 3 curing
1.9 1.9 accelerator A curing 2.7 2.7 accelerator B curing 2.2 2.2
accelerator C carnauba wax 1 1 1 1 1 1 1 1 1 1 antimony 6 6 6 6 6 6
6 6 6 6 trioxide carbon black 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6
2.6 epoxy silane 11 11 11 11 11 11 11 11 11 11 molten silica 1400
1400 1401 1407 1403 1361 1361 1362 1368 1364 molten silica 88 88 88
88 88 88 88 88 88 88 (% by weight)
[0252]
13 TABLE 13 example comparative example example comparative example
mixing material 58 59 76 77 78 60 61 79 80 81 epoxy resin 8 100 100
100 100 100 epoxy resin 9 100 100 100 100 100 curing agent 8 86 86
86 86 86 79 79 79 79 79 curing 2.1 2.1 accelerator 1 curing 2.1 2.1
accelerator 3 curing 2.2 2.2 accelerator A curing 3.1 3.1
accelerator B curing 2.5 2.5 accelerator C carnauba wax 1 1 1 1 1 1
1 1 1 1 antimony 6 6 6 6 6 6 6 6 6 6 trioxide carbon black 2.6 2.6
2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 epoxy silane 11 11 11 11 11 11 11
11 11 11 molten silica 1533 1533 1534 1540 1536 1478 1478 1479 1485
1481 molten silica 88 88 88 88 88 88 88 88 88 88 (% by weight)
[0253] The curing resin compositions of Example and Comparative
Examples were evaluated by the following tests. Tables 14 to 26
represent the results of evaluation.
[0254] The curing resing compositions were molded under conditions
of the temperature of a metal mold of 180.degree. C., the molding
pressure of 6.9 MPa and the curing time of 90 seconds by a transfer
molding machine. The post-curing was performed for 6 hours at
175.degree. C.
[0255] (1) Spiral Flow (Index of a Flow)
[0256] Flow distance (cm) was measured by molding the curing resin
composition using a metal mold for spiral flow measurement
according to EMMI-1-66 under the conditions.
[0257] (2) Hot Hardness
[0258] The curing resin compositions were molded in a disc having a
diameter of 50 mm and a thickness of 3 mm under the conditions.
After molded, the hot hardness of the discs was immediately
measured by using a shore D hardness meter.
[0259] (3) Hot Hardness Under Moisture Absorption
[0260] After the curing resin compositions were left for 72 hours
under the conditions of 25.degree. C./50% RH, the hot hardness was
measured by using the shore D hardness meter on the condition as
the above (2).
[0261] (4) Reflow Cracking Resistance: 1
[0262] The package of a QFP of 80 pins having an external size of
14.times.20.times.2.0 mm in which a silicon chip for test of the
size 8.times.10.times.0.4 mm on a 42 alloy frame was mounted by
using the silver paste was molded and post-cured by using the
curing resin composition under the conditions. After the package
was moisturized under the conditions of 85% RH and 30.degree. C.
for 168 hours, a reflow process was performed under the conditions
of 215.degree. C. for 90 seconds by a vapor phase reflow device,
and the presence of generation of crack was confirmed. Reflow
cracking resistance was evaluated by the number of cracked package
based on the number (5) of test package.
[0263] (5) Reflow Cracking Resistance: 2
[0264] Reflow cracking resistance was evaluated under the same
conditions as the above (4) except that the packages were
moisturized under the conditions of 60% RH and 85.degree. C. for
168 hours.
[0265] (6) Reflow Cracking Resistance: 3
[0266] Reflow cracking resistance was evaluated under the same
conditions as the above (4) except that the packages were
moisturized under the conditions of 85% RH and 85.degree. C. for
168 hours.
[0267] (7) High-temperature Storage Characteristics
[0268] A test device was used in which an aluminum wiring having a
line/space of 10 .mu.m was formed on a silicon substrate having an
oxidation film of a thickness 5 .mu.m and having an external shape
size of 5.times.9 mm and. The test device was mounted with a silver
paste on a 16 pins type DIP (Dual Inline Package) 42 alloy lead
frame to which partial silver plating is applied. Packages in which
bonding pads of the device and inner leads were connected in Au
lines by a thermonic wire at 200.degree. C. were molded under the
conditions by using the curing resin composition, and post-cured.
After storing the packages under the conditions of 200.degree. C.
for 500 hours and 1000 hours, the packages were taken out, and a
continuity test was performed. The number of defective packages was
examined, and high-temperature storage characteristics was
evaluated by the number of defective packages based on the number
(10) of the test packages.
14TABLE 14 evaluation example comparative example item 1 2 3 4 5 6
7 1 2 3 4 5 6 7 spiral flow 110 108 111 109 111 109 108 74 100 108
105 Mold- 107 69 hot hardness 83 82 83 83 84 83 84 80 79 83 83 ing
75 81 hot hardness 82 81 82 82 83 82 83 66 63 82 82 was 64 10 under
moisture impos- absorption sible reflow cracking 0/5 0/5 0/5 0/5
0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 resistance 1 reflow cracking
0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 resistance 2
reflow cracking 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5
resistance 3 high-temp. 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10
0/10 0/10 0/10 0/10 0/10 storage characteristics 500 h 1000 h 0/10
0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 10/10 10/10 0/10 10/10
[0269]
15TABLE 15 evaluation example comparative example item 8 9 10 11 12
13 14 8 9 10 11 12 13 14 spiral flow 121 120 122 119 121 120 118 73
95 116 118 Mold- 105 66 hot hardness 80 79 80 80 81 80 81 77 76 80
80 ing 70 78 hot hardness 79 78 79 79 80 79 80 63 55 79 79 was 45 0
under moisture impos- absorption sible reflow cracking 0/5 0/5 0/5
0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 resistance 1 reflow
cracking 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5
resistance 2 reflow cracking 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5
0/5 0/5 0/5 0/5 resistance 3 high-temp. 0/10 0/10 0/10 0/10 0/10
0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 storage characteristics 500
h 1000 h 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 10/10 10/10
0/10 10/10
[0270]
16TABLE 16 evaluation example comparative example item 15 16 17 18
19 20 21 15 16 17 18 19 20 21 spiral flow 110 111 112 110 113 110
108 70 97 109 107 Mold- 104 68 hot hardness 78 77 78 78 79 78 79 74
73 78 78 ing 65 76 hot hardness 76 75 76 76 77 76 77 55 48 76 76
was 40 0 under moisture impos- absorption sible reflow cracking 0/5
0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 resistance 1 reflow
cracking 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5
resistance 2 reflow cracking 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5
0/5 0/5 0/5 0/5 resistance 3 high-temp. 0/10 0/10 0/10 0/10 0/10
0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 storage characteristics 500
h 1000 h 0/10 0/10 0/10 0/10 10/10 0/10 0/10 0/10 0/10 10/10 10/10
0/10 10/10
[0271]
17TABLE 17 evaluation example comparative example example
comparative example item 22 23 22 23 24 24 25 25 26 27 spiral flow
105 104 71 98 101 106 104 72 97 101 hot hardness 82 82 80 79 82 79
79 76 75 79 hot hardness 81 81 66 63 81 78 77 62 58 78 under
moisture absorption reflow cracking 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5
0/5 0/5 resistance 1 reflow cracking 0/5 0/5 0/5 0/5 0/5 0/5 0/5
0/5 0/5 0/5 resistance 2 reflow cracking 0/5 0/5 0/5 0/5 0/5 0/5
0/5 0/5 0/5 0/5 resistance 3 high-temp. 0/10 0/10 0/10 0/10 0/10
0/10 0/10 0/10 0/10 0/10 storage characteristics 500 h 1000 h 0/10
0/10 0/10 0/10 10/10 0/10 0/10 0/10 0/10 10/10
[0272]
18TABLE 18 evaluation example comparative example example
comparative example item 26 27 28 29 30 28 29 31 32 33 spiral flow
103 104 72 97 100 101 102 69 98 99 hot hardness 80 80 78 77 80 84
84 82 81 84 hot hardness 79 78 62 59 79 83 83 69 66 83 under
moisture absorption reflow cracking 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5
0/5 0/5 resistance 1 reflow cracking 0/5 0/5 0/5 0/5 0/5 0/5 0/5
0/5 0/5 0/5 resistance 2 reflow cracking 0/5 0/5 0/5 0/5 0/5 0/5
0/5 0/5 0/5 0/5 resistance 3 high-temp. 0/10 0/10 0/10 0/10 0/10
0/10 0/10 0/10 0/10 0/10 storage characteristics 500 h 1000 h 0/10
0/10 0/10 0/10 10/10 0/10 0/10 0/10 0/10 10/10
[0273]
19TABLE 19 evaluation example comparative example example
comparative example item 30 31 34 35 36 32 33 37 38 39 spiral flow
104 104 74 99 101 103 104 73 98 101 hot hardness 82 82 80 79 82 81
81 78 77 81 hot hardness 81 81 66 63 81 80 80 63 59 80 under
moisture absorption reflow cracking 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5
0/5 0/5 resistance 1 reflow cracking 0/5 0/5 0/5 0/5 0/5 0/5 0/5
0/5 0/5 0/5 resistance 2 reflow cracking 0/5 0/5 0/5 0/5 0/5 0/5
0/5 0/5 0/5 0/5 resistance 3 high-temp. 0/10 0/10 0/10 0/10 0/10
0/10 0/10 0/10 0/10 0/10 storage characteristics 500 h 1000 h 0/10
0/10 0/10 0/10 10/10 0/10 0/10 0/10 0/10 10/10
[0274]
20TABLE 20 evaluation example comparative example example
comparative example item 34 35 40 41 42 36 37 43 44 45 spiral flow
102 103 63 94 99 100 101 64 95 87 hot hardness 82 82 81 80 82 82 82
80 79 82 hot hardness 81 80 67 65 81 81 81 65 63 81 under moisture
absorption reflow cracking 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5
resistance 1 reflow cracking 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5
0/5 resistance 2 reflow cracking 0/5 0/5 0/5 0/5 0/5 5/5 5/5 5/5
5/5 5/5 resistance 3 high-temp. 0/10 0/10 0/10 0/10 0/10 0/10 0/10
0/10 0/10 0/10 storage characteristics 500 h 1000 h 0/10 0/10 0/10
0/10 10/10 0/10 0/10 0/10 0/10 10/10
[0275]
21 TABLE 21 example comparative example example comparative example
evaluation item 38 39 46 47 48 40 41 49 50 51 spiral flow 102 101
65 94 98 98 97 61 91 84 hot hardness 80 80 79 78 80 86 86 85 84 86
hot hardness under 79 78 60 56 79 86 86 76 72 86 moisture
absorption reflow cracking 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5
resistance 1 reflow cracking 0/5 0/5 0/5 0/5 0/5 5/5 5/5 5/5 5/5
5/5 resistance 2 reflow cracking 5/5 5/5 5/5 5/5 5/5 5/5 5/5 5/5
5/5 5/5 resistance 3 high-temp. storage 0/10 0/10 0/10 0/10 0/10
0/10 0/10 0/10 0/10 0/10 characteristics 500 h 1000 h 0/10 0/10
0/10 0/10 10/10 0/10 0/10 0/10 0/10 10/10
[0276]
22 TABLE 22 example comparative example example comparative example
evaluation item 42 43 52 53 54 44 45 55 56 57 spiral flow 100 101
63 94 96 99 98 60 91 94 hot hardness 84 84 82 81 84 80 80 78 77 80
hot hardness under 83 83 69 66 83 79 79 59 54 79 moisture
absorption reflow cracking 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5
resistance 1 reflow cracking 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5
0/5 resistance 2 reflow cracking 5/5 5/5 5/5 5/5 5/5 5/5 5/5 5/5
5/5 5/5 resistance 3 high-temp. storage 0/10 0/10 0/10 0/10 0/10
0/10 0/10 0/10 0/10 0/10 characteristics 500 h 1000 h 0/10 0/10
0/10 0/10 10/10 0/10 0/10 0/10 0/10 10/10
[0277]
23 TABLE 23 example comparative example example comparative example
evaluation item 46 47 58 59 60 48 49 61 62 63 spiral flow 105 103
72 98 101 112 113 75 103 109 hot hardness 84 84 81 80 84 82 82 80
79 82 hot hardness under 83 83 68 65 83 81 81 66 62 81 moisture
absorption reflow cracking 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5
resistance 1 reflow cracking 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5
0/5 resistance 2 reflow cracking 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5
0/5 0/5 resistance 3 high-temp. storage 0/10 0/10 0/10 0/10 0/10
0/10 0/10 0/10 0/10 0/10 characteristics 500 h 1000 h 0/10 0/10
0/10 0/10 10/10 0/10 0/10 0/10 0/10 10/10
[0278]
24 TABLE 24 example comparative example example comparative example
evaluation item 50 51 64 65 66 52 53 67 68 69 spiral flow 106 104
75 99 102 99 100 65 92 95 hot hardness 84 84 82 81 84 87 87 86 85
87 hot hardness under 83 83 70 66 83 87 87 79 76 87 moisture
absorption reflow cracking 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5
resistance 1 reflow cracking 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5
0/5 resistance 2 reflow cracking 5/5 5/5 5/5 5/5 5/5 5/5 5/5 5/5
5/5 5/5 resistance 3 high-temp. storage 0/10 0/10 0/10 0/10 0/10
0/10 0/10 0/10 0/10 0/10 characteristics 500 h 1000 h 0/10 0/10
0/10 0/10 10/10 0/10 0/10 0/10 0/10 10/10
[0279]
25 TABLE 25 example comparative example example comparative example
evaluation item 54 55 70 71 72 56 57 73 74 75 spiral flow 110 108
80 103 106 108 107 78 102 105 hot hardness 83 82 80 79 83 82 81 78
77 82 hot hardness under 82 81 71 69 82 81 80 65 63 81 moisture
absorption reflow cracking 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5
resistance 1 reflow cracking 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5
0/5 resistance 2 reflow cracking 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5
0/5 0/5 resistance 3 high-temp. storage 0/10 0/10 0/10 0/10 0/10
0/10 0/10 0/10 0/10 0/10 characteristics 500 h 1000 h 0/10 0/10
0/10 0/10 10/10 0/10 0/10 0/10 0/10 10/10
[0280]
26 TABLE 26 example comparative example example comparative example
evaluation item 58 59 76 77 78 60 61 79 80 81 spiral flow 106 104
75 99 102 99 100 65 92 95 hot hardness 82 81 78 77 82 81 81 75 73
81 hot hardness under 81 80 68 66 81 80 80 63 59 80 moisture
absorption reflow cracking 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5
resistance 1 reflow cracking 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5
0/5 resistance 2 reflow cracking 0/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5
0/5 0/5 resistance 3 high-temp. storage 0/10 0/10 0/10 0/10 0/10
0/10 0/10 0/10 0/10 0/10 characteristics 500 h 1000 h 0/10 0/10
0/10 0/10 10/10 0/10 0/10 0/10 0/10 10/10
[0281] Examples 1 to 61 which contain the curing accelerator for a
curing resin of the invention were superior in the flow properties,
the storage stability, the hot hardness, the hot hardness under
moisture absorption, the reflow cracking resistance and the
high-temperature storage characteristics.
[0282] On the other hand, Comparative Examples 1-81 which does not
contain the curing accelerator for a curing resin of the invention
were inferior in at least one of the storage stability, the hot
hardness, the hot hardness under moisture absorption, the reflow
cracking resistance and the high-temperature storage
characteristics as compared with Examples having the same resin
composition.
* * * * *